CN108330452A - The preparation method of MAX phase coatings - Google Patents

The preparation method of MAX phase coatings Download PDF

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Publication number
CN108330452A
CN108330452A CN201810029528.XA CN201810029528A CN108330452A CN 108330452 A CN108330452 A CN 108330452A CN 201810029528 A CN201810029528 A CN 201810029528A CN 108330452 A CN108330452 A CN 108330452A
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coatings
sources
coating
preparation
deposition
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王振玉
李文涛
柯培玲
张栋
汪爱英
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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
    • 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

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Abstract

The present invention relates to the preparation methods of MAX phase coatings, include the following steps：One substrate is provided, M A X coatings are deposited on the surface of substrate using cathodic arc ion plating method combination magnetically controlled sputter method, wherein, cathode arc target provides the sources M, and M is transiting group metal elements in the sources M, magnetic controlled sputtering target provides the sources A, A is Al elements or Si elements in the sources A, and reaction gas provides the sources X, and X is C element or N element in the sources X, and there is the substrate of M A X coatings to make annealing treatment deposition, obtain MAX phase coatings.The present invention is alternatively formed rich M element coating and rich element A coating using cathodic arc ion plating method combination magnetically controlled sputter method, M atoms are in close-packed hexagonal structure in wherein rich M element coating, C atoms or N atoms are solid-solution in close-packed hexagonal structure, there is similar crystal structure with MAX phase coatings, therefore, in annealing, the formation temperature of MAX phases can be reduced, reduces the damage to substrate.

Description

The preparation method of MAX phase coatings
Technical field
The present invention relates to ceramic coating technical fields, more particularly to the preparation method of MAX phase coatings.
Background technology
In recent years, with the rapid development of the relevant industries such as nuclear power, aerospace, ocean, to structural material it is anti-oxidant, The requirement of corrosion resistance is higher and higher.Coating technology is widely used for improving structural material in a manner of its economy, simplicity Anti-oxidant and corrosion resistance.Currently, surface-coating technology is mainly using magnetron sputtering and cathodic arc ion plating technology as representative Physical gas-phase deposite method, deposit various anti-oxidant, corrosion-resistant coatings in different structure material surface, as metal, carbide, Nitride and FeCrAl coatings etc..
Ternary layered ceramic MAX phases are a kind of novel metalloid ceramic materials, and wherein M is transition metal, typical such as Ti, Cr, V etc.；A is then major element, commonly uses such as Al, Si；X is C or N.MAX phases belong to P63/mmc space groups, crystal structure It is alternately arranged and is formed by nearly closely packed M6X octahedral layers and A atomic layers.Unique layer structure makes MAX phases have both metal With ceramics excellent properties, such as：Excellent electric conductivity and thermal conductivity, good anti-thermal shock and damage tolerance, lower hardness and Preferable machining property, higher elasticity modulus and elevated temperature strength and outstanding inoxidizability and corrosion resistance etc..With This simultaneously, MAX phases also embody good radiation-damage stability energy.It is wide that a series of this excellent performance makes MAX phase materials have Wealthy application prospect.Up to the present, also relatively difficult due to synthesizing large-sized MAX phases block materials, limit MAX phases Practical application, therefore the synthesis of MAX phase coatings receives the extensive concern of people.
The preparation method of traditional MAX phases coating mainly has spray coating method and physical vapour deposition (PVD) (PVD).Wherein spray coating method is made Standby coating structure is quite loose, is unfavorable for the later stage for high-temperature oxydation and corrosion.Therefore, the preparation of MAX phases at present is with physics Based on vapor deposition.Physical vapour deposition (PVD) can be divided into two kinds according to the difference of concrete technology：(direct high temperature is heavy for one-step method Product) and two-step method (room temperature deposition+thermal annealing).Wherein, magnetron sputtering technique (MS) and cathodic arc ion plating are directly utilized (CVA) etc. when one-step method depositing coating, requirement of the high preparation temperature to equipment is harsher, thus is difficult to realize the work of coating Industry application.And two-step method is because can depositing coating and subsequent annealing can be at ambient temperature that the preparation of MAX phases carries It is widely used at phase temperature range for broader.
However, due to MAX phases itself have larger c-axis value, 211 phases (c~1.3nm), 312 phases (c~1.8nm), 413 The unit cell dimension of phase (c~2.3-2.4nm) is sequentially increased, and the diffusion length of required atom increases in preparation process, preparation temperature Also it increases successively.Such as usual two-step method prepares high-crystallinity Ti2The annealing temperature of AlC coatings concentrates on 650 DEG C or more, has Even as high as 750 DEG C or more.However, excessively high annealing temperature is microcosmic to common metal base material (titanium alloy, zircaloy etc.) Structure and mechanical property can be caused compared with macrolesion.
Invention content
Based on this, it is necessary to which, in view of the above-mentioned problems, providing a kind of preparation method of MAX phases coating, which uses Cathodic arc ion plating method combination magnetically controlled sputter method deposits M-A-X coatings, and anneals to M-A-X coatings.The preparation Method is not necessarily to too high annealing temperature, smaller to the damage of substrate, and the MAX phases obtained have high-purity and high crystalline, open up The application range of MAX phase coatings is opened up.
A kind of preparation method of MAX phases coating, the preparation method comprises the following steps：
One substrate is provided；
M-A-X coatings are deposited on the surface of the substrate using cathodic arc ion plating method combination magnetically controlled sputter method, Wherein, cathode arc target provides the sources M, and M is transiting group metal elements in the sources M, and magnetic controlled sputtering target provides the sources A, and A is Al members in the sources A Element or Si elements, reaction gas provide the sources X, and X is C element or N element in the sources X；And
There is the substrate of the M-A-X coatings to make annealing treatment deposition, obtains MAX phase coatings.
Only single method uses cathodic arc ion plating or magnetron sputtering, required annealing temperature compared with the existing technology For higher, the present invention using cathodic arc ion plating method combination magnetically controlled sputter method due to being alternatively formed rich M element coating With rich element A coating.The rich M element coating being alternatively formed and rich element A coating can be realized mutually uniform by annealing steps Diffusion, and obtain more uniform MAX phase coatings.M atoms in wherein rich M element coating are in close-packed hexagonal structure, C atoms or N atoms are solid-solution in close-packed hexagonal structure, after annealing, obtain the MAX phases.The obtained MAX phases with it is existing Technology is formed by MAX phases by single method has similar crystal structure.Due to rich M element coating and rich element A coating In being periodically alternatively formed, therefore, in annealing, it is only necessary to which lower annealing temperature can be realized M, element A and fully mutually expand It dissipates and ultimately forms MAX phase coatings, greatly reduce the formation temperature of MAX phases.As a result, because the temperature of annealing is without too high, into And the damage to substrate is reduced, therefore the application range of MAX phase coatings can be expanded.
Description of the drawings
Fig. 1 is the surface transmission electron microscope picture of 1 obtained Ti-Al-C coatings of the embodiment of the present invention；
Fig. 2 is that the surface transmission electron microscope figure line of 1 obtained Ti-Al-C coatings of the embodiment of the present invention sweeps result Figure；
Fig. 3 is the X-ray diffraction spectrogram of the obtained MAX phases coating of embodiment 1 to 4 in the present invention；
Fig. 4 is the X-ray diffraction spectrogram that MAX phase coatings are made in embodiment 5 in the present invention；
Fig. 5 is the X-ray diffraction spectrogram that MAX phase coatings are made in embodiment 6 in the present invention.
Specific implementation mode
The technical solution in embodiment of the present invention will be clearly and completely described below, it is clear that described reality The mode of applying is only some embodiments of the invention, rather than whole embodiments.Based on the embodiment in the present invention, All other embodiment that those of ordinary skill in the art are obtained without creative efforts belongs to this Invent the range of protection.
The present invention provides a kind of preparation method of MAX phases coating.The preparation method comprises the following steps：
S1 provides a substrate；
S2 is applied using cathodic arc ion plating method combination magnetically controlled sputter method in the surface of substrate deposition M-A-X Layer, wherein cathode arc target provides the sources M, and M is transiting group metal elements in the sources M, and magnetic controlled sputtering target provides the sources A, and A is Al in the sources A Element or Si elements, reaction gas provide the sources X, and X is C element or N element in the sources X；And
S3 has the substrate of the M-A-X coatings to make annealing treatment deposition, obtains MAX phase coatings.
Since the above-mentioned sources A are Al elements or Si elements, when providing the sources A according to cathode arc target, the knot of rich element A coating Structure is especially loose, when especially the sources A are Al elements；Moreover, Al targets are difficult to adopt cathodic arc ion plating technology.Therefore, this hair It is bright to provide the sources A using magnetic controlled sputtering target.
In step sl, the material of the substrate is unlimited.Preferably, the substrate is Zr alloys, Ti alloys, stainless steel In one kind.
In step s 2, the process of the deposition M-A-X coatings includes multiple deposition cycles, in each deposition cycle In, the cathodic arc ion plating method is used alternatingly with magnetically controlled sputter method.
In step s 2, total number of cycles >=25 of the deposition cycle.I.e.：Rich M element coating described in MAX phase coatings and Coating amts >=50 layer of the richness element A coating.
In each deposition cycle of step S2, rich M element coating is deposited using the cathodic arc ion plating method Any restriction is not done with the sedimentary sequence for depositing rich element A coating using magnetically controlled sputter method, can first deposit rich M element coating Redeposited richness element A coating can also first deposit the redeposited rich M element coating of rich element A coating.
In each deposition cycle of step S2, the rich M element coating of cathodic arc ion plating method deposition when Between be 5s~20s, the time of the rich element A coating of magnetically controlled sputter method deposition is 5s~20s.In view of first in annealing process Element diffusion is more abundant, it is preferred that the sedimentation time of rich M element coating and rich element A coating is 5s~10s.
In each deposition cycle of step S2, the thickness of the richness M element coating is 10nm~20nm, the richness A The thickness of first element coating is 5nm~10nm.In conjunction with deposition cycle sum, i.e.,：Thickness >=375nm of MAX phase coatings.
In step s 2, the electric current of cathode arc target is 45A~65A, the magnetic in the cathodic arc ion plating method The target power output for controlling magnetic controlled sputtering target in sputtering method is 2.9kW~3.5kW, and the bias of the substrate is -100V~-300V.It examines Consider the difference of arc technology and magnetic control technology itself sputter rate, it is preferred that cathode arc in cathodic arc ion plating method The electric current of target is 45A~50A, and the target power output of magnetic controlled sputtering target is 3.2kW~3.5kW in magnetically controlled sputter method.
In step s 2, the reaction gas be passed through flow be the standard milliliters of 100 standard milliliters/minute~300/point Clock, reaction gas include nitrogen or hydrocarbon gas, and the percent by volume in the reaction gas shared by nitrogen or hydrocarbon gas is 2%~10%.In view of after annealing generate MAX phases purity, it is preferred that be passed through gas flow be 100 standard milliliters/minute~ Percent by volume shared by 200 standard milliliters/minute, nitrogen or hydrocarbon gas is 5%~8%.
In step s 2, in the deposition process of M-A-X coatings, the time of temperature≤300 DEG C of deposition, deposition is 60min~240min.In view of MAX phases are in the advantage of field of corrosion prevention, it is preferred that sedimentation time 180min~240min.
In step s 2, before depositing M-A-X coatings, first a transition zone is deposited on the surface of the substrate, wherein institute It is the transiting group metal elements layer to state transition zone.In view of coating and the thermally matched influence of matrix, the preferably described transition zone Transiting group metal elements are identical with the M element in the M-A-X coatings.
In step s3, the temperature of the annealing is 500 DEG C~600 DEG C, time of annealing be 15h~ 300h.By long-time process annealing, element A is made fully to diffuse to form MAX phase coatings, greatly reduces the formation temperature of MAX phases Degree, and under identical annealing temperature, annealing time extends, and MAX phase purity is higher.Thus, it can get by extending annealing time High-purity, high crystalline MAX phases also can suitably reduce annealing temperature by extending annealing time, further decrease high annealing Influence of the temperature to substrate.In view of making the more abundant of elements diffusion, the crystallinity of coating is improved, it is preferred that annealing Time be 50h~200h.
In step s3, the annealing carries out under conditions of vacuum or argon gas are protected, wherein the vacuum it is true Reciprocal of duty cycle is 1.0 × 10-3Pa~3.0 × 10-2The ar pressure of Pa, the argon gas protection are 0.5~1.5 atmospheric pressure.It considers To reduce oxygen content in coating, it is preferred that the vacuum degree of vacuum is 2.0 × 10-3Pa~3.0 × 10-2Pa, the argon of argon gas protection Gas air pressure is 1.0~1.5 atmospheric pressure.
Only single use cathodic arc ion plating or magnetron sputtering, required annealing temperature are higher compared with the existing technology For, the present invention using cathodic arc ion plating method combination magnetically controlled sputter method due to being alternatively formed rich M element coating and richness A First element coating, wherein the M atoms in rich M element coating are in close-packed hexagonal structure, C atoms or N atoms are solid-solution in close-packed hexagonal knot In structure, there is similar crystal structure with MAX phase coatings, therefore, in annealing, it is only necessary to which lower annealing temperature can be realized M, the abundant phase counterdiffusion of element A and ultimately form MAX phase coatings, greatly reduce the formation temperature of MAX phases.And then due to annealing Temperature without too high, reduce the damage to substrate, therefore the application range of MAX phase coatings can be expanded.
The present invention uses the chemical formula for the MAX phase coatings that above-mentioned preparation method obtains for Mn+1AXn, in formula, M is transition group Metallic element, A are Al elements or Si elements, and X is C element or N element, the integer that n is 1~6.Preferably, the MAX phases coating For Ti2AlC、Ti2AlN、Ti3AlC2、V2AlC、Ti4AlC3、Cr2AlC、Zr2AlC、Zr3Al3C5、Zr2Al4C5、Ti3SiC2In one Kind.
The M-A-X coatings obtained using above-mentioned preparation method in annealing, the abundant phase counterdiffusion of M element, element A and it is final Form MAX phase coatings, M element in MAX phase coatings, the concentration distribution of element A in increasing concen-trations/successively decrease cyclically-varying.It should The defects of MAX phases coating is without hole, column crystal boundary and crackle, and the surface bulky grain of MAX phase coatings is few, meanwhile, relative to The prior art is for only single use cathodic arc ion plating or magnetron sputtering obtain MAX phases at relatively high temperatures, this method Using lower annealing temperature, avoid the generation of dephasign under high temperature, therefore, the purity higher of MAX phase coatings, reach 95% with On.
Hereinafter, will be described further to described MAX phases coating and preparation method thereof by following specific examples.
Embodiment 1：
(1) the zircaloy substrate after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) depositing Ti transition zone is used, the electric current of electric arc target is 60A, and argon flow amount is 200 standards Ml/min, deposition thickness 350nm.
(4) use cathodic arc ion plating method combination magnetically controlled sputter method in the surface depositing Ti-Al-C of Ti transition zones Coating, wherein cathode arc target provides the sources Ti, and magnetic controlled sputtering target provides the sources Al, reaction gas CH4The sources C are provided.Base period It is respectively placed in rotation in front of cathode arc target and magnetic controlled sputtering target, that is, cathodic arc ion plating method is used alternatingly and is splashed with magnetic control Shooting method is in the surface of Ti transition zones deposition richness Ti members element coating and deposition richness Al member element coatings, the richness Ti in a deposition cycle The sedimentation time of first element coating is 5s, and the sedimentation time of thickness 10nm, rich Al members element coating are 5s, thickness 5nm, cathode electricity The target power output of the electric current 50A of arc target, magnetic controlled sputtering target are 3.2kW, CH4Flow is 15 standard milliliters/minute, and argon flow amount is The bias of 200 standard milliliters/minute, control pressure 4Pa, substrate is -200V, and the temperature of deposition is 200 DEG C, and sedimentation time is 1.5h。
The substrate of depositing Ti-Al-C coatings is heat-treated under (5) atmospheric pressure argon gas protective conditions, heating rate For 5 DEG C/min, annealing temperature is 600 DEG C, and soaking time is respectively 15h.
The surface transmission electron microscope picture of Ti-Al-C coatings is as shown in Figure 1 before annealing.The surface of Ti-Al-C coatings is saturating It penetrates electron microscope component lines and sweeps that the results are shown in Figure 2.By Fig. 1 and Fig. 2 it is found that Ti-Al-C coatings be one kind by rich Ti elements Coating and richness Al member element coatings form multicycle laminated construction.
Coating X-ray diffraction spectrogram after annealing is as shown in Figure 3.From the figure 3, it may be seen that prepared coating passes through at 600 DEG C After 15h annealing, Ti has been obtained2AlC (002) and Ti2The MAX phase coatings of AlC (103), thickness are about 9 μm.
Embodiment 2：
Embodiment 2 is differed only in embodiment 1, and the annealing temperature of embodiment 2 is 600 DEG C, and soaking time is respectively 20h.Coating X-ray diffraction spectrogram after annealing is as shown in figure 3, obtained the better Ti of crystallinity2The MAX phases of AlC apply Layer, thickness is about 9 μm.
Embodiment 3：
Embodiment 3 is differed only in embodiment 1, and the annealing temperature of embodiment 3 is 600 DEG C, and soaking time is respectively 50h.Coating X-ray diffraction spectrogram after annealing is as shown in figure 3, obtained the superior Ti of crystallinity2The MAX phases of AlC apply Layer, thickness is about 9 μm.
From the figure 3, it may be seen that in embodiment 1 to 3, with the extension of annealing time, Ti2The peak intensity and crystallinity of AlC constantly increases By force, Al atoms permeatings can be made in coating and constantly at mutually crystallizing by illustrating annealing time extension, MAX phase purity highers.
Embodiment 4：
Embodiment 4 is differed only in embodiment 1, and the annealing temperature of embodiment 4 is 580 DEG C, and soaking time is respectively 50h.Coating X-ray diffraction spectrogram after annealing when at 580 DEG C as shown in figure 3, from the figure 3, it may be seen that after 50h anneals, obtain Ti2The MAX phase coatings of AlC (002), thickness are about 9 μm.It compares with embodiment 1, under conditions of annealing temperature reduces, Enough energy can be provided for Al atoms permeatings to overcome energy barrier by extension annealing time, therefore can be at low temperature Obtain MAX phases.Therefore, at 580 DEG C of even lower temperature, Ti can be further increased by extending annealing time2AlC is applied The phase purity and crystallinity of layer.
Embodiment 5：
(1) the zircaloy substrate after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) is used to deposit Cr transition zones, the electric current of electric arc target is 60A, and argon flow amount is 50 standards Ml/min, air pressure 4Pa, deposition thickness 400nm.
(4) cathodic arc ion plating method combination magnetically controlled sputter method is used to deposit Cr-Al-C on the surface of Cr transition zones Coating, wherein cathode arc target provides the sources Cr, and magnetic controlled sputtering target provides the sources Al, reaction gas CH4The sources C are provided.Base period It is respectively placed in rotation in front of electric arc target and magnetic control target, that is, cathodic arc ion plating method is used alternatingly and exists with magnetically controlled sputter method The surface deposition richness Cr members element coating and deposition richness Al member element coatings of Cr transition zones, in a deposition cycle, rich Cr elements apply The sedimentation time of layer is 15s, and the sedimentation time of thickness 20nm, rich Al members element coating are 10s, thickness 10nm, cathode arc The target power output of the electric current 50A of target, magnetic controlled sputtering target are 3.2kW, CH4Flow is 15 standard milliliters/minute, argon flow amount 200 The bias of standard milliliters/minute, control pressure 4Pa, substrate is -200V, and the temperature of deposition is 200 DEG C, sedimentation time 3h.
The substrate for depositing Cr-Al-C coatings is heat-treated under (5) atmospheric pressure argon gas protective conditions, heating rate For 5 DEG C/min, holding temperature is 500 DEG C, soaking time 60h.
Coating X-ray diffraction spectrogram after annealing when at 500 DEG C as shown in figure 4, after 60h anneals, obtain Cr2The MAX phase coatings of AlC, thickness are about 8 μm.
Embodiment 6：
(1) the zircaloy substrate after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) depositing Ti transition zone is used, the electric current of electric arc target is 60A, and argon flow amount is 50 standards Ml/min, air pressure 4Pa, deposition thickness 400nm.
(4) use cathodic arc ion plating method combination magnetically controlled sputter method in the surface depositing Ti-Al-N of Ti transition zones Coating, wherein cathode arc target provides the sources Ti, and magnetic controlled sputtering target provides the sources Al, reaction gas N2The sources N are provided.Base period It is respectively placed in rotation in front of electric arc target and magnetic control target, that is, cathodic arc ion plating method is used alternatingly and exists with magnetically controlled sputter method The surface deposition richness Ti members element coating and deposition richness Al member element coatings of Ti transition zones, in a deposition cycle, rich Ti elements apply The sedimentation time of layer is 15s, and the sedimentation time of thickness 15nm, rich Al members element coating are 10s, thickness 8nm, cathode arc target Electric current 60A, the target power output of magnetic controlled sputtering target is 3.2kW, N2Flow is 10 standard milliliters/minute, and argon flow amount is 190 standards The bias of ml/min, control pressure 4Pa, substrate is -200V, and the temperature of deposition is 200 DEG C, sedimentation time 3.5h.
The substrate of depositing Ti-Al-N coatings is heat-treated under (5) atmospheric pressure argon gas protective conditions, heating rate For 5 DEG C/min, holding temperature is 600 DEG C, soaking time 50h.
Coating X-ray diffraction spectrogram after annealing after the 50h that anneals at 600 DEG C as shown in figure 5, it is found that obtained crystallinity Preferable Ti2The MAX phase coatings of AlN.
Embodiment 7：
(1) titanium alloy substrate after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) depositing Ti transition zone is used, the electric current of electric arc target is 60A, and argon flow amount is 50 standards Ml/min, air pressure 4Pa, deposition thickness 400nm.
(4) use cathodic arc ion plating method combination magnetically controlled sputter method in the surface depositing Ti-Si-C of Ti transition zones Coating, wherein cathode arc target provides the sources Ti, and magnetic controlled sputtering target provides the sources Si, reaction gas CH4The sources C are provided.Base period It is respectively placed in rotation in front of electric arc target and magnetic control target, that is, cathodic arc ion plating method is used alternatingly and exists with magnetically controlled sputter method The surface deposition richness Ti members element coating and deposition richness Si member element coatings of Ti transition zones, in a deposition cycle, rich Ti elements apply The sedimentation time of layer is 20s, and the sedimentation time of thickness 20nm, rich Si members element coating are 20s, thickness 10nm, cathode arc The target power output of the electric current 65A of target, magnetic controlled sputtering target are 3.5kW, CH4Flow is 6 standard milliliters/minute, and argon flow amount is 294 marks The bias of quasi- ml/min, control pressure 4Pa, substrate is -300V, and the temperature of deposition is 100 DEG C, sedimentation time 4h.
(5) it is 2.0 × 10 in vacuum degree-3The substrate of depositing Ti-Si-C coatings is heat-treated under the conditions of Pa, heating speed Rate is 5 DEG C/min, and holding temperature is 600 DEG C, soaking time 100h, has obtained the preferable Ti of crystallinity3SiC2MAX phases apply Layer.
Embodiment 8：
(1) the zircaloy substrate after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) is used to deposit V transition zones, the electric current of electric arc target is 60A, and argon flow amount is 50 standards milli Liter/min, air pressure 4Pa, deposition thickness 400nm.
(4) cathodic arc ion plating method combination magnetically controlled sputter method is used to be applied in the surface of V transition zones deposition V-Al-C Layer, wherein cathode arc target provides the sources V, and magnetic controlled sputtering target provides the sources Al, reaction gas CH4The sources C are provided.Base period point It is not placed in rotation in front of electric arc target and magnetic control target, that is, cathodic arc ion plating method is used alternatingly with magnetically controlled sputter method in V The rich V element coating of surface deposition and deposition richness Al member element coatings of transition zone, in a deposition cycle, rich V element coating Sedimentation time is 10s, thickness 10nm, and the sedimentation time of rich Al members element coating is 15s, thickness 10nm, cathode arc target The target power output of electric current 45A, magnetic controlled sputtering target are 3.0kW, CH4Flow is 16 standard milliliters/minute, and argon flow amount is 184 standards The bias of ml/min, control pressure 4Pa, substrate is -100V, and the temperature of deposition is 150 DEG C, sedimentation time 3h.
(5) it is 3.0 × 10 in vacuum degree-2The substrate for depositing V-Al-C coatings is heat-treated under conditions of Pa, is heated up Rate is 5 DEG C/min, and holding temperature is 550 DEG C, soaking time 200h, has obtained the preferable V of crystallinity2The MAX phases of AlC apply Layer.
Embodiment 9：
(1) the stainless steel base after cleaning, drying is put into vacuum cavity.
(2) argon gas of 100 standard milliliters/minute is passed through to vacuum chamber, it is 0.2A that linear anode ion ource electric current, which is arranged, Substrate bias is -300V, and 40min is performed etching to substrate using the argon ion of ionization.
(3) arc ion plating (aip) is used to deposit Zr transition zones, the electric current of electric arc target is 60A, and argon flow amount is 50 standards Ml/min, air pressure 4Pa, deposition thickness 400nm.
(4) cathodic arc ion plating method combination magnetically controlled sputter method is used to deposit Zr-Al-C on the surface of Ti transition zones Coating, wherein cathode arc target provides the sources Zr, and magnetic controlled sputtering target provides the sources Al, reaction gas CH4The sources C are provided.Base period It is respectively placed in rotation in front of electric arc target and magnetic control target, that is, cathodic arc ion plating method is used alternatingly and exists with magnetically controlled sputter method The surface deposition richness Zr members element coating and deposition richness Al member element coatings of Zr transition zones, in a deposition cycle, rich Zr elements apply The sedimentation time of layer is 10s, and the sedimentation time of thickness 10nm, rich Al members element coating are 10s, thickness 5nm, cathode arc target Electric current 50A, the target power output of magnetic controlled sputtering target is 2.9kW, CH4Flow is 10 standard milliliters/minute, and argon flow amount is 90 standards The bias of ml/min, control pressure 4Pa, substrate is -200V, and the temperature of deposition is 200 DEG C, sedimentation time 1h.
(5) it is 1.0 × 10 in vacuum degree-3The substrate for depositing Zr-Al-C coatings is heat-treated under conditions of Pa, is heated up Rate is 5 DEG C/min, and holding temperature is 500 DEG C, soaking time 300h, has obtained the preferable Zr of crystallinity2The MAX phases of AlC Coating.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of preparation method of MAX phases coating, which is characterized in that the preparation method comprises the following steps：
One substrate is provided；
M-A-X coatings are deposited on the surface of the substrate using cathodic arc ion plating method combination magnetically controlled sputter method, wherein Cathode arc target provides the sources M, and M is transiting group metal elements in the sources M, and magnetic controlled sputtering target provides the sources A, and A is Al elements or Si in the sources A Element, reaction gas provide the sources X, and X is C element or N element in the sources X；And
There is the substrate of the M-A-X coatings to make annealing treatment deposition, obtains MAX phase coatings.
2. the preparation method of MAX phases coating according to claim 1, which is characterized in that the mistake of the deposition M-A-X coatings Journey includes multiple deposition cycles, and in each deposition cycle, the cathodic arc ion plating method is handed over magnetically controlled sputter method For use.
3. the preparation method of MAX phases coating according to claim 2, which is characterized in that the period of the deposition cycle is total Number >=25.
4. the preparation method of MAX phases coating according to claim 2, which is characterized in that in each deposition cycle, adopt The time that rich M element coating is deposited with the cathodic arc ion plating method is 5s~20s, heavy using the magnetically controlled sputter method The time of product richness element A coating is 5s~20s.
5. the preparation method of MAX phases coating according to claim 4, which is characterized in that in each deposition cycle, institute The thickness for stating rich M element coating is 10nm~20nm, and the thickness of the richness element A coating is 5nm~10nm.
6. the preparation method of MAX phases coating according to claim 1, which is characterized in that the cathodic arc ion plating side The electric current of cathode arc target is 45A~65A in method, in the magnetically controlled sputter method target power output of magnetic controlled sputtering target be 2.9kW~ The bias of 3.5kW, the substrate are -100V~-300V.
7. the preparation method of MAX phases coating according to claim 1, which is characterized in that the reaction gas is passed through stream Amount is 100 standard milliliters/minute~300 standard milliliters/minute, and the reaction gas includes nitrogen or hydrocarbon gas, described anti- It is 2%~10% to answer the percent by volume shared by nitrogen in gas or hydrocarbon gas.
8. the preparation method of MAX phases coating according to claim 1, which is characterized in that in the deposition process of M-A-X coatings In, the time of temperature≤300 DEG C of deposition, deposition is 60min~240min.
9. the preparation method of MAX phases coating according to claim 1, which is characterized in that before depositing M-A-X coatings, First a transition zone is deposited on the surface of the substrate, wherein the transition zone is the transiting group metal elements layer.
10. the preparation method of MAX phases coating according to claim 1, which is characterized in that the temperature of the annealing is 500 DEG C~600 DEG C, the time of annealing is 15h~300h.
CN201810029528.XA 2018-01-12 2018-01-12 The preparation method of MAX phase coatings Pending CN108330452A (en)

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CN111748782A (en) * 2019-03-29 2020-10-09 中国科学院宁波材料技术与工程研究所 MAX phase coating and preparation method thereof
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CN115522169A (en) * 2022-09-30 2022-12-27 广东工业大学 Composite deposition method of oxide hard coating and coated cutter
CN116607108A (en) * 2023-07-18 2023-08-18 中国科学院宁波材料技术与工程研究所 MAX-Ag conductive composite coating and preparation method thereof
CN116607108B (en) * 2023-07-18 2023-12-08 中国科学院宁波材料技术与工程研究所 MAX-Ag conductive composite coating and preparation method thereof

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Application publication date: 20180727