CN118064834A - Solid solution MAX phase coating resistant to high-temperature vapor corrosion and preparation method and application thereof - Google Patents

Solid solution MAX phase coating resistant to high-temperature vapor corrosion and preparation method and application thereof Download PDF

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Publication number
CN118064834A
CN118064834A CN202410484091.4A CN202410484091A CN118064834A CN 118064834 A CN118064834 A CN 118064834A CN 202410484091 A CN202410484091 A CN 202410484091A CN 118064834 A CN118064834 A CN 118064834A
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max phase
solid solution
alc
functional layer
temperature vapor
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Inventor
王振玉
张安峰
汪爱英
马冠水
颜景军
许钰玺
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/0635—Carbides
    • 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
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • 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
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
    • F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
    • F23R3/28—Continuous combustion chambers using liquid or gaseous fuel characterised by the fuel supply
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
    • G21C3/02—Fuel elements
    • G21C3/04—Constructional details
    • G21C3/06—Casings; Jackets
    • G21C3/07—Casings; Jackets characterised by their material, e.g. alloys

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Abstract

The invention discloses a solid solution MAX phase coating resistant to high-temperature vapor corrosion, a preparation method and application thereof, wherein the solid solution MAX phase coating comprises a TiAl transition layer and a (Ti, nb) 2 AlC MAX phase functional layer; the (Ti, nb) 2 AlC MAX phase functional layer is deposited on the TiAl transition layer in a mode of combining high-power pulse magnetron sputtering and direct-current magnetron sputtering. The MAX phase coating has better high-temperature vapor corrosion resistance.

Description

Solid solution MAX phase coating resistant to high-temperature vapor corrosion and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal surface protection, and particularly relates to a solid solution MAX phase coating resistant to high-temperature vapor corrosion, a preparation method and application thereof.
Background
The high-temperature steam corrosion can be generated when a water loss accident (LOCA) occurs, so that the Zr alloy cladding is accelerated to be oxidized violently to cause failure, wherein advanced coating materials are adopted for surface modification, and the purpose of providing longer service life for the Zr alloy cladding in a high-temperature steam environment is achieved.
The MAX phase is a ternary lamellar compound of the general formula M n+1AXn, which has a typical weak metal bond between M and A atoms, and forms a covalent bond in the M n+1Xn layer. n=1-3, and represents 211, 312 and 413 phases, respectively. The M-position includes the early transition metal and a portion of the rare earth element, the a-position includes IIIA, IV and some late transition metal elements, x=c or N.
The MAX phase exhibits a combination of metal and ceramic properties such as good workability, good electrical and thermal conductivity, excellent oxidation resistance, and strong corrosion resistance due to the presence of metallic and covalent bonds in the MAX phase. Therefore, the MAX phase has great potential application value in the fields of ocean engineering, aerospace, thermoelectric materials and the like.
At present, because a compact continuous Al 2O3 passivation film is easy to form in Ti-based MAX phase Ti 2 AlC, the inward diffusion of oxygen is inhibited, and the oxidation resistance and corrosion resistance of the material can be greatly improved.
The invention patent application with publication number of CN115491563A discloses a novel MAX phase porous material (Ti aZrbNbcTadCreMof)2 AlC and a preparation method thereof, which comprises the following steps of taking transition metal simple substance powder (two or more than two of Ti, zr, nb, ta, cr, mo, al), al powder and graphite powder with a certain atomic proportion as raw materials, fully mixing the raw materials with zirconia balls with different diameters, placing the mixed powder under a press machine, obtaining a green body by controlling different pressing pressures and dwell times, and finally sintering the green body to obtain the novel MAX phase porous material.
However, the materials provided by the above patent oxidize various elements in high temperature environment to different extent, and the defects of pores, cracks and the like are caused by the mismatch of thermal expansion coefficients between the oxides, so that the corrosive medium is accelerated to penetrate inwards to cause the materials to fail in advance. The material has high porosity and poor protection effect, and is not beneficial to being applied in a high-temperature environment. Although the resistance of Ti 2 AlC to high-temperature vapor corrosion can be improved by increasing the Al content, exceeding the Al content in a certain range results in difficulty in phase formation of Ti 2 AlC.
Therefore, there is a need to design a Ti-based MAX-phase film that can achieve high temperature vapor corrosion resistance.
Disclosure of Invention
The invention provides a solid solution MAX phase coating resistant to high-temperature vapor corrosion, which has better high-temperature vapor corrosion resistance.
A solid solution MAX phase coating resistant to high temperature vapor corrosion, the solid solution MAX phase coating comprising a TiAl transition layer and a (Ti, nb) 2 AlC MAX phase functional layer;
And the (Ti, nb) 2 AlC MAX phase functional layer is deposited on the TiAl transition layer by a mode of combining high-power pulse magnetron sputtering and direct-current magnetron sputtering and then annealing.
According to the invention, the (Ti, nb) 2 AlC MAX phase functional layer can be densely and firmly deposited on the TiAl transition layer by high-power pulse magnetron sputtering and direct-current magnetron sputtering technologies, so that the peeling can be prevented, and meanwhile, the corrosion resistance can be enhanced due to the compact surface.
According to the invention, nb replaces part of Ti at the M position, so that Al element can be efficiently utilized in a high-temperature vapor environment, and loss of the Al element is reduced as much as possible, so that the Al element diffused to the outer layer can form a continuous Al 2O3 film with proper thickness, growth of a non-protective oxide film TiO 2 is inhibited, corrosion speed of a (Ti, nb) 2 AlC MAX phase functional layer is greatly reduced, and service life of a solid-solution MAX phase coating is remarkably prolonged.
The invention adopts the concept of M-site solid solution, and the high-valence metal atoms replace the low-valence metal atoms, so that the number of oxygen vacancies can be reduced, and the inward diffusion of O and the outward diffusion of Ti are restrained, thereby restraining the growth of the non-protective film. Nb is used as a high-valence element, has similar atomic radius and electronegativity to Ti, can realize infinite solid solution of Nb, and is favorable for promoting the formation of Al 2O3 under the high-temperature condition, and further improves the resistance of the coating to water vapor corrosion, so that the Ti 2 AlC coating is subjected to solid solution strengthening by adopting Nb.
Preferably, the (Ti, nb) 2 AlC MAX phase functional layer is an equiaxed crystal.
Because the (Ti, nb) 2 AlC MAX phase functional layer provided by the invention is equiaxed crystal, the equiaxed crystal has uniform and dense structure, can effectively prevent corrosion medium from penetrating into the material, reduces the corrosion rate of the material, has relatively uniform structure and no obvious grain boundary and grain direction, can reduce the penetration and corrosion of the corrosion medium at the grain boundary, thereby improving the corrosion resistance of the material, and can reduce the risk of stress corrosion cracking due to the fact that the equiaxed crystal lacks stress concentration points on the grain boundary.
Preferably, the mass fraction of Nb in the (Ti, nb) 2 alcmax phase functional layer is 5-30at.%. If the content of Nb is too low, a continuous Al 2O3 film with proper thickness cannot be formed on the surface of the coating in the high-temperature vapor corrosion process, the effect of TiO 2 is inhibited from being reduced, excessive defects are formed if the content of Nb is too high, corrosion channels are easily formed due to the existence of the excessive defects, the high-temperature corrosion resistance is poor, and the high content of Nb can also cause the MAX phase to be out of phase.
Preferably, the (Ti, nb) 2 AlC MAX phase functional layer is in a close-packed hexagonal structure.
Preferably, the (Ti, nb) 2 AlC MAX phase functional layer is composed of a MA layer with weak bond bonding and an MX layer with strong bond bonding, where M is composed of Ti and Nb, a is Al, and X is C.
Preferably, the thickness ratio of the (Ti, nb) 2 AlC MAX phase functional layer to the TiAl transition layer is 5:1-40:1. A TiAl transition layer and a (Ti, nb) 2 AlC MAX phase functional layer with proper thickness, wherein Al element in the transition layer can diffuse into the functional layer and form a continuous alumina film in a high-temperature vapor environment; the TiAl transition layer with proper thickness can avoid the diffusion of matrix elements to the (Ti, nb) 2 AlC MAX phase functional layer at high temperature, and the TiAl transition layer with proper thickness can also prevent the (Ti, nb) 2 AlC MAX phase functional layer from falling off, thereby improving the bonding rate.
Preferably, the TiAl transition layer is columnar crystal.
Preferably, the TiAl transition layer has a close-packed hexagonal structure.
Preferably, the TiAl transition layer is columnar crystal and has a close-packed hexagonal structure.
According to the invention, columnar crystals are arranged between the matrix and the (Ti, nb) 2 AlC MAX phase functional layer, and the TiAl transition layer with a close-packed hexagonal structure is provided with Al element on the one hand, so that the (Ti, nb) 2 AlC MAX phase functional layer has proper amount of Al at high temperature to form an aluminum oxide film and inhibit the formation of titanium oxide, and the matrix element can be prevented from diffusing to the (Ti, nb) 2 AlC MAX phase functional layer, thereby adversely affecting the coating performance.
On the other hand, the invention also provides a preparation method of the solid solution MAX phase coating resistant to high-temperature vapor corrosion, which comprises the following steps:
s1, etching a substrate in a vacuum environment under Ar atmosphere; the purpose of the step S1 is to remove the surface pollution of the matrix and activate the surface, and enhance the combination with the transition layer;
s2, depositing a TiAl transition layer on the surface of the substrate in the step S1 by using a TiAl target through high-power pulse magnetron sputtering (HiPIMSI);
S3, in Ar and CH 4 atmosphere, using a TiAl target to perform high-power pulse magnetron sputtering, and simultaneously using a Nb target to perform direct-current magnetron sputtering, and depositing a Ti-Nb-Al-C functional layer grown by columnar crystal on the surface of the TiAl transition layer in the step S2;
And S4, carrying out vacuum annealing to enable the Ti-Nb-Al-C functional layer in the step S3 to carry out solid phase reaction to obtain the (Ti, nb) 2 AlC MAX phase functional layer.
The invention utilizes a high-power pulse power supply to combine with direct-current magnetron sputtering to realize the preparation of (Ti, nb) 2 AlC, the ionization rate of sputtering materials is improved by the lower duty ratio and the higher peak power density in high-power discharge, the kinetic energy of particles entering the surface of a substrate is enhanced, the deposited (Ti, nb) 2 AlC coating can be phased at a lower temperature in the subsequent heat treatment process, the phase-forming temperature range of the traditional MAX phase block is 1000-1200 ℃, the direct-current magnetron sputtering can realize the solid solution of trace Nb elements, the controllable preparation of different Nb contents (Ti, nb) 2 AlC can be realized, the solid solution (Ti, nb) 2 AlC coating prepared by the invention adopts double-target co-sputtering, compared with other technologies, the quantity of targets is reduced by adopting a gas carbon source, the bonding force and the stability of the coating can be improved, and the invention is environment-friendly and safe.
Preferably, the etching conditions of step S1 are: the temperature of the cavity where the substrate is located is 150-300 ℃, the pressure of the cavity is 1.4-2.3 mTorr, the Ar gas flow is 35-60 sccm, the ion source voltage is 1000-1200V, the substrate is biased to-300V to-150V, and the plasma glow etching time is 30-60 min.
Preferably, the power of the high-power pulse magnetron sputtering in the step S2 is 1800-2100W, the pulse width is 100-200 mu S, and the duty ratio is 5% -10%.
Preferably, in the step S2, the flow rate of Ar is 80-100 sccm, the substrate bias voltage is-200V-150V, the pressure of the cavity is 2.5-3.4 mTorr, and the deposition time is 20-60 min.
Preferably, the power of the high-power pulse magnetron sputtering in the step S3 is 1800-2100W, the pulse width is 100-200 mu S, the duty ratio is 5% -10%, and the power of the direct-current magnetron sputtering is 200-450W.
Preferably, the flow rate of the CH 4 is 2-5 sccm, the substrate bias voltage is-150V to-75V, the cavity air pressure is 2.7-3.7 mTorr, and the deposition time is 1-9 hours.
Preferably, the conditions of vacuum annealing are: the vacuum degree reaches 2X 10 -4~3×10-3 Pa at room temperature, the annealing temperature is 700-900 ℃, the heating rate is 8-15 ℃/min, and the annealing time is 1-5 h. Magnetron sputtering already provides a certain energy, so the annealing temperature provided by the invention is lower.
On the other hand, the invention also provides application of the solid solution MAX phase coating resistant to high-temperature vapor corrosion in aero-engine blades, combustor nozzles and accident-tolerant fuel cladding.
Compared with the prior art, the invention has the beneficial effects that:
The invention forms a compact (Ti, nb) 2 AlC MAX phase functional layer on the TiAl transition layer by utilizing a mode of combining high-power pulse magnetron sputtering and direct-current magnetron sputtering, and can also enable a proper amount of Nb to be solid-dissolved in the MAX phase, and the corrosion resistance of the (Ti, nb) 2 AlC MAX phase functional layer in the environment of high-temperature vapor is improved due to the actions of the compact functional layer and Nb elements solid-dissolved in the compact functional layer.
According to the invention, the high-valence metal Nb replaces part of low-valence Ti to be in solid solution in the MAX phase, so that oxygen vacancies and Ti vacancies of TiO 2 are reduced in the environment of high-temperature steam, oxygen inward diffusion and Ti outward diffusion are restrained, and doping of Nb also promotes outward diffusion of Al to form a continuous protective alumina film, so that a small amount of Al can form the alumina film to reduce loss of Al, and the formed corrosion layer is thinner, is more compact, has fewer defects, greatly reduces corrosion rate, and remarkably improves service life.
Drawings
FIG. 1 shows XRD patterns of (Ti, nb) 2 AlC MAX functional phase coating prepared in example 1 of the present invention.
FIG. 2 is a SEM image of the surface morphology of a (Ti, nb) 2 AlC MAX functional phase coating prepared in example 1 of the present invention.
FIG. 3 is an XRD spectrum of the (Ti, nb) 2 AlC MAX phase coating prepared in example 1 of the present invention after corrosion.
FIG. 4 is a SEM image of the cross-sectional morphology of the (Ti, nb) 2 AlC MAX phase coating prepared in example 1 of the present invention after 30 min etching at 1000 ℃.
Fig. 5 is an XRD spectrum of the coating provided in comparative example 1 after 30min of corrosion at 1000 ℃.
FIG. 6 is a SEM spectrum of the cross-sectional morphology of the coating provided in comparative example 1 after 30 min Corrosion at 1000 ℃.
FIG. 7 is a graph showing the weight gain of the coatings provided in examples 1, 2,3,4 and comparative examples 1, 2,3 of the present invention after 30min of corrosion at 1000 ℃.
FIG. 8 is a TEM image of the (Ti, nb) 2 AlC MAX phase functional layer obtained in example 1 of the present invention.
Detailed Description
Detailed description of the applicationthe present application is described in detail with reference to specific embodiments thereof, but the present application is not limited to the described embodiments.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The embodiment of the application shows the following method:
analyzing the phase composition of the coating before and after corrosion by using an X-ray diffractometer (XRD);
Observing and analyzing the morphology and composition of the coating before and after corrosion by using a Scanning Electron Microscope (SEM);
the growth pattern of the coating was observed using a Transmission Electron Microscope (TEM).
Example 1: in this embodiment, the substrate material is Ti 6Al4 V titanium alloy, and the specific preparation method of the (Ti, nb) 2 AlC MAX phase coating on the substrate surface is as follows:
s1, polishing the Ti 6Al4 V titanium alloy matrix to a mirror surface by using silicon carbide metallographic sand paper. The substrates were each washed 15 min a by acetone and ethanol in sequence and then placed in a deposition chamber.
S2, heating the deposition chamber to 150 ℃, when the vacuum degree of the chamber is pumped to be lower than 3 multiplied by 10 -5 Torr, introducing 35 sccm high-purity Ar into the vacuum deposition chamber, applying-200V bias voltage to the substrate, and performing 30 min plasma glow etching on the surface of the substrate, wherein the chamber pressure is 1.4 mTorr.
S3, a TiAl transition layer is deposited on the surface of a substrate by using a TiAl target and adopting a high-power pulse magnetron sputtering (HiPIMS) technology, 100 sccm of high-purity Ar is introduced into a cavity, the bias voltage of the substrate is-150V, the power is 2000W, the pulse width is 100 mu S, the duty ratio is 5%, the pressure of the cavity is 3.4 mTorr, and the deposition time of the Ti-Al transition layer is 30 min.
S4, adopting a high-power pulse magnetron sputtering (HiPIMS) technology and combining direct-current magnetron sputtering (DCMS) to deposit a (Ti, nb) 2 AlC coating on the surface of the transition layer. 3 sccm of high-purity CH 4 reaction gas is introduced to provide carbon atoms, ar flow is 100 sccm, power, pulse width and duty ratio of the TiAl target are the same as those of the step S3, the Nb target adopts a direct current magnetron sputtering method, the power of the direct current magnetron sputtering is set to 400W, the cavity pressure is 3.6 mTorr, and the deposition time of the Ti-Nb-Al-C coating is 5 h.
S5, placing the deposited sample in a tube furnace, heating the sample to 750 ℃ at a heating speed of 10 ℃/min when the vacuum degree is pumped to be less than 3 x 10 -4 Pa, preserving heat for 90 min, and naturally cooling to room temperature to obtain the (Ti, nb) 2 AlC MAX phase coating, wherein the Nb doping content is 22%.
FIGS. 1 and 2 are XRD patterns and surface morphology patterns, respectively, of the (Ti, nb) 2 AlC MAX coating prepared in this example 1. The (Ti, nb) 2 AlC coating mainly comprises (Ti, nb) 2 AlC and a small amount of Ti 3 Al, and the coating is compact and uniform and has no obvious defects.
Fig. 3 and 4 are XRD patterns and cross-sectional morphology patterns of the (Ti, nb) 2 AlC MAX coating prepared in this example 1, respectively, after 1000 ℃ corrosion for 30: 30 min. After corrosion, the solid solution MAX phase is the main phase, but the very obvious non-protective oxides TiO 2 and TiO are generated, meanwhile, the generation of protective oxide Al 2O3 is detected, the corrosion layer is compact and uniform without obvious defects, the corrosion layer is thinner, the thickness is about 894 and nm, and continuous and compact Al 2O3 exists on the surface of the corrosion layer.
Fig. 8 is a TEM image of the (Ti, nb) 2 AlC MAX phase coating prepared in this example 1, and after annealing, the coating structure is dense, and the (Ti, nb) 2 AlC is grown as equiaxed crystals.
Example 2: unlike example 1, in this example, the sputtering power of the Nb target was adjusted to 350W in step S4, and the remainder was 17% in Nb doping content as in example 1.
Example 3: unlike example 1, in this example, the sputtering power of the Nb target was adjusted to 300W in step S4, and the remainder was 12% in Nb doping content as in example 1.
Example 4: unlike example 1, in this example, the sputtering power of the Nb target was adjusted to 200W in step S4, and the remainder was the same as in example 1, with a Nb doping content of 5%.
Comparative example 1: this example is a comparative example of example 1 described above. The only difference between comparative example 1 and example 1 is that: in step 4 of comparative example 1, the Nb target power was not applied any more when the functional layer was deposited, and other conditions were the same as in the example.
S1, polishing a Ti6Al4V titanium alloy substrate to a mirror surface by using silicon carbide metallographic sand paper, sequentially cleaning the substrate by using acetone and ethanol respectively for 15 min, and then placing the substrate into a deposition chamber.
S2, heating the temperature of the deposition chamber to 150 ℃, when the vacuum degree of the chamber is pumped to below 3x 10 -4 Pa, introducing 35: 35 sccm high-purity Ar into the vacuum deposition chamber, applying a bias voltage of-200: 200V to the substrate, and performing 30: 30 min plasma glow etching on the surface of the substrate.
S3, a TiAl transition layer is deposited on the surface of a substrate by using a TiAl target and adopting a high-power pulse magnetron sputtering (HiPIMS) technology, 100 sccm of high-purity Ar is introduced into the chamber, the substrate bias voltage is-150V, the power is 2000W, the pulse width is 100 mu S, the duty ratio is 5%, and the deposition time of the TiAl transition layer is 30 min.
S4, depositing a Ti 2 AlC MAX coating on the surface of the transition layer by adopting a high-power pulse magnetron sputtering (HiPIMS) technology, and introducing 3 sccm high-purity CH 4 reaction gas to provide carbon atoms, wherein the power, pulse width and duty ratio of the TiAl target are unchanged, and the deposition time of the Ti-Al-C coating is 5 h.
S5, placing the deposited sample in a tube furnace, heating the sample to 750 ℃ at a heating speed of 10 ℃/min when the vacuum degree is pumped to be less than 3 x 10 -4 Pa, preserving heat for 90 min, and naturally cooling to room temperature to obtain the Ti 2 AlC MAX phase coating.
Fig. 5 and 6 are an XRD spectrum and a cross-sectional morphology of the Ti 2 AlC MAX coating prepared in comparative example 1, respectively, after 30min of 1000 ℃ corrosion. After corrosion, the MAX phase almost disappeared, tiO 2 was the main phase, and TiO 2 grew preferentially at (110) high, and the formation of Al 2O3 was detected. The corrosion layer of the coating is thicker, about 6 mu m is formed, the coating has defects such as pores, the surface layer TiO 2 is a main oxide, and the bottom of the Al 2O3 with TiO 2 causes the weakening of the protective capability of the coating. Therefore, the coating of the invention greatly improves the high-temperature water vapor corrosion resistance of Ti 2 AlC, inhibits the growth of non-protective oxide films, promotes the formation of continuous and compact Al 2O3 on the surface, and can reduce the thickness of the corrosion layer to 1/6 of the original thickness and the weight gain to 1/8 of the Ti 2 AlC.
Comparative example 2: this example is a comparative example of example 1 described above. The only difference between comparative example 2 and example 1 is: in step 4 of comparative example 2, the sputtering power of the Nb target was adjusted to 80W, and the other conditions were the same as in the examples. Nb content was 1.7%, and corrosion mass gain was 2.51 mg/cm 2. The corrosion resistance of the coating is not significantly improved.
Comparative example 3: this example is a comparative example of example 1 described above. The only difference between comparative example 3 and example 1 is: in step S4, the sputtering power of the Nb target was adjusted to 600W, and the Nb doping content was 45% in the same manner as in example 1. The corrosion mass gain was 1.82 mg/cm 2, an increase in weight relative to example 1 due to the increased coating defects caused by the higher Nb content, increasing the in-diffusion of the corrosive medium.
FIG. 7 is a graph showing the mass gain after corrosion of examples 1,2, 3,4 and comparative examples 1,2, 3, the mass gain after Nb doping is significantly reduced, and the corrosion gains of examples 1-4 are 1/8, 1/7, 1/4 and 1/3 of Ti 2 AlC, respectively. Comparative example 2 shows that when the Nb content is too small, the corrosion resistance of the coating is not significantly improved, and comparative example 3 shows that when the Nb content is too large, the corrosion resistance of the coating starts to deteriorate.

Claims (10)

1. The solid solution MAX phase coating resistant to high-temperature vapor corrosion is characterized by comprising a TiAl transition layer and a (Ti, nb) 2 AlC MAX phase functional layer;
And the (Ti, nb) 2 AlC MAX phase functional layer is deposited on the TiAl transition layer by a mode of combining high-power pulse magnetron sputtering and direct-current magnetron sputtering and then annealing.
2. The solid solution MAX phase coating resistant to high temperature vapor corrosion according to claim 1, wherein said (Ti, nb) 2 AlC MAX phase functional layer is equiaxed.
3. The solid solution MAX phase coating resistant to high temperature vapor corrosion according to claim 1, wherein the Nb content in said (Ti, nb) 2 AlC MAX phase functional layer is 5-30at.%.
4. The solid solution MAX phase coating resistant to high temperature vapor corrosion according to claim 1, wherein said (Ti, nb) 2 AlC MAX phase functional layer is a close packed hexagonal structure.
5. The high temperature vapor corrosion resistant solid solution MAX phase coating according to claim 1, wherein said (Ti, nb) 2 AlC MAX phase functional layer comprises a MA layer with weak bond bonding and a MX layer with strong bond bonding, wherein M comprises Ti and Nb, a is Al, and X is C.
6. The high temperature vapor corrosion resistant solid solution MAX phase coating according to claim 1, wherein the thickness ratio of (Ti, nb) 2 AlC MAX phase functional layer to TiAl transition layer is 5:1-40:1.
7. The high temperature vapor corrosion resistant solid solution MAX phase coating according to claim 1, wherein said TiAl transition layer is columnar crystalline and is in a close packed hexagonal structure.
8. A method of preparing a high temperature vapor corrosion resistant solid solution MAX phase coating according to any one of claims 1-7, comprising:
S1, etching a substrate in a vacuum environment under Ar atmosphere;
S2, depositing a TiAl transition layer on the surface of the substrate in the step S1 by using a TiAl target through high-power pulse magnetron sputtering;
S3, in Ar and CH 4 atmosphere, using a TiAl target to perform high-power pulse magnetron sputtering, and simultaneously using a Nb target to perform direct-current magnetron sputtering, and depositing a Ti-Nb-Al-C functional layer grown by columnar crystal on the surface of the TiAl transition layer in the step S2;
And S4, carrying out vacuum annealing to enable the Ti-Nb-Al-C functional layer in the step S3 to carry out solid phase reaction to obtain the (Ti, nb) 2 AlC MAX phase functional layer.
9. The method for preparing a solid solution MAX phase coating resistant to corrosion by high temperature vapor according to claim 8, wherein the vacuum annealing conditions are: the vacuum degree reaches 2X 10 -4~3×10-3 Pa at room temperature, the annealing temperature is 700-900 ℃, the heating rate is 8-15 ℃/min, and the annealing time is 1-5 h.
10. Use of a solid solution MAX phase coating resistant to high temperature vapor corrosion according to any one of claims 1-7 in aero-engine blades, combustor nozzles and accident tolerant fuel cladding.
CN202410484091.4A 2024-04-22 2024-04-22 Solid solution MAX phase coating resistant to high-temperature vapor corrosion and preparation method and application thereof Pending CN118064834A (en)

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