CN115142017A - Is suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection and preparation method and application thereof - Google Patents

Is suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection and preparation method and application thereof Download PDF

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CN115142017A
CN115142017A CN202210691349.9A CN202210691349A CN115142017A CN 115142017 A CN115142017 A CN 115142017A CN 202210691349 A CN202210691349 A CN 202210691349A CN 115142017 A CN115142017 A CN 115142017A
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tial
sublayer
nano
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protection
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文懋
和香伶
王龙鹏
何星嘉
张侃
郑伟涛
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Jilin University
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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
    • C23C14/34—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

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Abstract

The invention discloses Ti 3 Ti alloy surface modification technology field 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection comprises a modulation unit consisting of a plurality of alternating metal sublayers, wherein the modulation unit comprises a TiAl sublayer and a Cr sublayer; the scheme adopts a magnetron sputtering technology and adopts a magnetron sputtering method on Ti 3 TiAl/Cr metal nano multilayer film with excellent high-temperature performance is prepared on Al alloy, wherein a TiAl nano sublayer is formed by the TiAl nano sublayer and Ti 3 The same chemical components of the Al matrix provide excellent interface compatibility and interface bonding force, the higher aluminum content provides higher high-temperature strength and oxidation resistance, the Cr nano sublayer simultaneously and obviously improves the hardness and toughness of the TiAl nano sublayer, and the Cr nano sublayer alternately existsThe sublayer can induce the formation of a compact two-dimensional nano-layered oxide layer in a high-temperature air environment, and the problem of a loose oxide layer during high-temperature oxidation of a single TiAl coating is solved.

Description

Is suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection and preparation method and application thereof
Technical Field
The invention relates to Ti 3 The technical field of Al alloy surface modification, in particular to a titanium alloy suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multi-layer coating for Al protection and a preparation method and application thereof.
Background
Ti 3 The Al alloy is an excellent high-temperature structural material in the range of 650-700 ℃ due to excellent properties of light weight, high strength, high temperature resistance, high temperature creep resistance and the like, and is widely applied to the fields of aeroengine compressor wheel discs, structural parts of blades, hypersonic aircraft skins and the like. Ti reinforced by SiC fibers 3 Al-based composite material with Ti 3 Compared with the Al matrix, the Al matrix has higher high-temperature specific strength and specific stiffness, and can further increase the service temperature to be more than 800 ℃. At this time, ti in the composite material 3 The Al matrix is subjected to more severe environmental erosion, severe oxidation can occur particularly in a high-temperature environment, and bar-shaped TiO appears at high temperature due to insufficient aluminum content in the system 2 Oxidation products, destroying the continuous compact Al 2 O 3 Layer formation (usually with an Al content of more than 59% it is possible to form a protective continuous Al 2 O 3 Layer) which also limits SiC fiber reinforced Ti 3 The Al-based composite material is directly applied to the high-temperature field. Therefore, how to solve the problem of SiC fiber reinforced Ti 3 Ti-based composite material in service 3 The serious high-temperature oxidation problem of Al alloy and the guarantee of good mechanical property of the alloy at high temperature become one of the key engineering problems.
Currently, surface modified coating technology is one of the effective solutions, and the common coating system comprises a ceramic coating and a metal coating, wherein the ceramic coating has high hardness, excellent high temperature resistance, but has low ductility and Ti 3 Poor compatibility of Al alloy limits its use as protective coating on Ti 3 Al alloyApplication range on gold. While another class of metallic high temperature oxidation resistant coatings (of which NiCrAlY superalloy coatings are the typical representative) has good high temperature oxidation resistance, the Ni element in the coating reacts with Ti at high temperature 3 Al alloy can generate serious element interdiffusion, which seriously reduces the mechanical property of the alloy and influences the interface bonding capability of the coating and the alloy.
Thus with Ti 3 The TiAl system with the same chemical composition of Al alloy attracts wide attention, and the TiAl coating system not only satisfies the requirement of good compatibility with the alloy, but also is better than Ti 3 The Al alloy has higher aluminum content and more excellent high-temperature oxidation resistance. Although a single TiAl coating has good oxidation resistance, tiO 2 And Al 2 O 3 The oxidation products still have strong competitive relationship, the oxidation resistance of the oxidation products needs to be further improved, high brittleness can be brought due to high aluminum content of the oxidation products, the high-temperature oxidation resistance and toughness of the TiAl-based coating are improved, and the problem that SiC fiber reinforced Ti is effectively solved 3 The Al-based composite material has serious oxidation problem under high-temperature environment.
Therefore, it is highly desirable to design a Ti alloy suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection and a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a Ti alloy suitable for Ti 3 A high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection and a preparation method and application thereof are provided to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: is suitable for Ti 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection comprises a modulation unit formed by a plurality of metal sublayers with alternating components, wherein the modulation unit comprises a TiAl sublayer and a Cr sublayer, and the TiAl sublayer and the Cr sublayer are both metal sublayers.
Further, the above applies to Ti 3 In the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection, the number of the modulation units>1, and when the number of the modulation units>1 hour, each timeAnd the units are arranged in a superposed manner.
Further, the above applies to Ti 3 In the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection, the thickness of the TiAl/Cr nano multilayer coating is 4-5 mu m.
Further, the above applies to Ti 3 In the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection, the thickness of the TiAl sublayer is 30-60 nm; the thickness of the Cr sub-layer is 1-50 nm.
Is suitable for Ti 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection comprises the following steps:
s1: placing the substrate on a sample frame, placing the sample frame into a film coating chamber of a magnetron sputtering device, mounting a TiAl target and a Cr target on a target position of the sputtering device, and vacuumizing a cavity;
s2: and opening the substrate to rotate, introducing argon, starting magnetron sputtering, and obtaining the TiAl/Cr metal nano multilayer film on the surface of the substrate after sputtering is finished.
Further, the above applies to Ti 3 In the preparation method of the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection, in the S1, the substrate is sequentially cleaned and dried before use; the cleaning is ultrasonic cleaning in acetone and ethanol in sequence.
Further, the above applies to Ti 3 In the preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection, in the S2, in the sputtering process, the surface of the substrate is parallel to the surface of a sputtering target material, and a TiAl target and a Cr target are arranged on corresponding target positions of a multi-target magnetron sputtering coating chamber to ensure that the surface of the substrate is parallel to the surface of the target material.
Further, the above applies to Ti 3 In the preparation method of the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection, in the S2, the sputtering current of the TiAl target is 1-3A'; the sputtering current of the Cr target is 0.1-3A.
Further, the above applies to Ti 3 In the preparation method of the high-temperature oxidation resistant TiAl/Cr nano multi-layer coating for Al protection, in the S2, the autorotation rate of the substrate is preferably 30-90r/h。
Compared with the prior art, the invention has the beneficial effects that:
the invention comprises a TiAl nano-sublayer and a Cr nano-sublayer, wherein the TiAl nano-sublayer is formed by combining Ti with the TiAl nano-sublayer 3 The same chemical composition of the Al matrix provides excellent interface compatibility and interface bonding force, the higher aluminum content provides higher high-temperature strength and oxidation resistance, the Cr nano sub-layer simultaneously and obviously improves the hardness and toughness of the TiAl nano sub-layer, and the alternately existing Cr nano sub-layers can induce the formation of a compact two-dimensional nano layered oxide layer in a high-temperature air environment, namely, the Cr nano sub-layer preferentially oxidizes at high temperature and preferentially captures the formation of lower aluminum elements (Cr, al) 2 O 3 The ternary compact oxide layer realizes the separation and rearrangement of titanium and aluminum elements, forms a multilayer compact oxide layer and leads the TiO growing in a rod shape to grow 2 The nano oxide layer is confined, so that the formation of a loose oxide layer is avoided; the metal nano multilayer film provided by the invention is firmly combined with the substrate, and the hardness, toughness and high-temperature oxidation resistance of the film can be obviously improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a TiAl/Cr metal nano-multilayer film on an alumina substrate prepared in example 1 of the present invention;
FIG. 2 is a schematic view of the TiAl/Cr metal nano-multilayer film structure on the alumina substrate prepared in example 2 of the present invention
FIG. 3 is a schematic cross-sectional view of SEM before and after oxidation in air at 800 ℃ for 1h of samples prepared in examples of the invention and comparative examples;
FIG. 4 is a schematic representation of SEM surface topography before and after oxidation in air at 800 ℃ for 1h for samples prepared in examples of the invention and comparative examples;
FIG. 5 is a schematic representation of a TEM cross-section of example 2 of the present invention after oxidation in air at 800 ℃ for 1 h;
FIG. 6 is a hardness profile and an indentation SEM image for example 1, example 2 and comparative example 2 of the present invention;
FIG. 7 is a schematic view of a TiAl/Cr metal nano multi-layer coating prepared by the present invention during high temperature oxidation;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: is suitable for Ti 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection comprises a modulation unit formed by a plurality of alternating metal sublayers, wherein the modulation unit comprises a TiAl sublayer and a Cr sublayer, and the TiAl sublayer and the Cr sublayer are both metal sublayers. Number of modulation units>1, and when the number of modulation units>1, the modulation units are arranged in a superposition mode. The thickness of the TiAl/Cr nano multilayer film is 4-5 mu m; the thickness of the TiAl sublayer is 30-60 nm; the thickness of the Cr sublayer is 1-50 nm.
In the invention, the number of the TiAl/Cr metal nano-multilayer film units is preferably 70-130, more preferably 80-120, and particularly preferably 90 and 100; the thickness ratio of the TiAl sublayer and the Cr sublayer in each unit is independently preferably 45; in a particular embodiment of the invention, the thickness of the TiAl sublayer is preferably 45nm and the thickness of the cr sublayer is preferably 5nm and 10nm.
The TiAl nano sublayer has Ti 3 The same chemical components of the Al matrix provide excellent interface compatibility and interface bonding force, the higher aluminum content provides higher high-temperature strength and oxidation resistance, and the Cr nano sublayer simultaneously and obviously improvesThe hardness and toughness of the TiAl nano-sublayer, and the alternately existing Cr nano-sublayers can induce the formation of a compact two-dimensional nano-layered oxide layer under the high-temperature air environment, namely, the Cr nano-sublayers preferentially oxidize and capture the formation of lower aluminum elements (Cr and Al) at high temperature 2 O 3 The ternary compact oxide layer realizes the separation and rearrangement of titanium and aluminum elements, forms a multilayer compact oxide layer and leads the TiO growing in a rod shape to grow 2 The nano oxide layer is confined, so that the formation of a loose oxide layer is avoided.
Is suitable for Ti 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection comprises the following steps:
s1: placing the substrate on a sample frame, placing the sample frame into a film coating chamber of a magnetron sputtering device, mounting a TiAl target and a Cr target on a target position of the sputtering device, and vacuumizing a cavity; the substrate is washed and dried in sequence before use; the cleaning is ultrasonic cleaning in acetone and ethanol in turn (the substrate is placed in acetone, alcohol and deionized water in turn for ultrasonic cleaning and then dried, in the invention, the ultrasonic cleaning time of the substrate in acetone and absolute ethanol is 15-20 min independently, the drying temperature is 40-60 ℃, and the drying time is 1-1.5 h preferably);
s2: opening the substrate to rotate, then introducing argon, starting magnetron sputtering, and obtaining a TiAl/Cr metal nano multilayer film on the surface of the substrate after sputtering is finished; in the sputtering process, the surface of the substrate is parallel to the surface of a sputtering target material, and a TiAl target and a Cr target are arranged on corresponding target positions of a multi-target magnetron sputtering coating chamber to ensure that the surfaces of the substrate and the target material are parallel; sputtering current of TiAl target is 1-3A; the sputtering current of the Cr target is 0.1-3A; the substrate rotation rate is preferably 30 to 90r/h. After sputtering is finished, the obtained film is cooled to room temperature under the vacuum condition to obtain the TiAl/Cr metal nano multilayer film.
The invention takes argon as sputtering gas, the purity of the argon is preferably 99.995-99.999%, and the flow rate of the argon is preferably 50-90 sccm, more preferably 60-80 sccm. The invention adopts magnetic control sputteringThe shooting technology uses TiAl target and Cr target as sputtering target materials to respectively target Ti 3 And (4) alternately sputtering the Al substrate to obtain the high-temperature antioxidant nano multilayer coating. Before the sputtering, the vacuum degree of the film coating chamber is preferably controlled to be better than 4 multiplied by 10 -4 Pa, the gas impurities in the coating chamber can be discharged to the maximum extent, and the oxidation in the coating process is avoided. In the present invention, the substrate surface is preferably parallel to the sputtering target surface, and specifically, it is preferably: and mounting the TiAl target and the Cr target on corresponding target positions of a multi-target magnetron sputtering coating chamber to enable the surfaces of the substrate and the target materials to be parallel. In the present invention, the working gas pressure during sputtering is preferably 0.5 to 1.2Pa, and more preferably 0.8Pa. The invention can ensure the optimal deposition rate by adopting the working air pressure. In the present invention, the rotation speed of the substrate holder during sputtering is preferably 30 to 90r/h, more preferably 60r/h. In the invention, the sputtering current of the TiAl target is preferably 1-3A, the voltage is preferably 300-450V, and the voltage is more preferably 375V; the sputtering current of the Cr target is preferably 0.1 to 3A, the voltage is preferably 200 to 400V, and the voltage is more preferably 284V; in the invention, the sputtering time of the high-temperature antioxidant nano multilayer coating is preferably 50-230 min, and more preferably 65-125 min.
Comparative example 1
Firstly, ti with phi of 18 x 2mm 3 And sequentially using 1000-mesh, 3000-mesh, 5000-mesh and 7000-mesh sandpaper to polish the Al sheet on a metal polishing machine until the surface is smooth and has no obvious scratch. And polishing the treated Ti 3 Putting the Al sheet in an acetone solvent, performing ultrasonic treatment for 20min, taking out, performing ultrasonic treatment for 20min with ethanol, and drying to obtain clean Ti 3 And an Al substrate.
Ti obtained in this example 3 Carrying out high-temperature oxidation experiment on the Al substrate, namely, cleaning Ti 3 The Al substrate is placed in a crucible and is placed in a tube furnace, an alumina heat insulation plug is placed at the sealing position, a flange is fastened, and the port is sealed. And then, turning on a power supply of the mechanical pump, adjusting a temperature rise program of the tube furnace, raising the temperature from room temperature to 800 ℃ at a temperature rise rate of 10 ℃/min, continuously operating the mechanical pump during the temperature rise period, avoiding over severe oxidation caused by overlong temperature rise time, keeping the temperature for one hour after the temperature rises to 800 ℃, turning off the mechanical pump, and simulating the oxidation condition of the mechanical pump in the air. Oxygen (O)And after the reaction is finished, closing the power supply of the tube furnace, and cooling the sample to room temperature along with the furnace.
For the oxidized Ti obtained in this example 3 SEM observation of the cross section and surface of the Al substrate, as shown in FIG. 3 (a) and FIG. 4 (a), ti 3 The Al substrate surface was covered with a thick oxide layer of about 1.75 μm. The oxidized surface showed a lot of ravines and cracks. This indicates that Ti is present 3 The Al substrate was strongly oxidized at 800 ℃.
Comparative example 2
Firstly, ti with phi of 18 x 2mm 3 The Al sheet is sequentially polished by 1000-mesh, 3000-mesh, 5000-mesh and 7000-mesh sand paper on a metal polishing machine until the surface is smooth and has no obvious scratch. Ti after polishing treatment 3 Putting the Al sheet in an acetone solvent, performing ultrasonic treatment for 20min, taking out, performing ultrasonic treatment for 20min with ethanol, and drying to obtain clean Ti 3 An Al substrate; fixing the cleaned substrate on a rectangular sample frame, and putting the substrate into a sample chamber of a multi-target magnetron sputtering device; respectively placing the TiAl alloy target and the Cr target in a multi-target magnetron sputtering device, and adjusting the target base distance to be 10cm.
After the preparation is finished, the vacuum cavity is closed, and the vacuum degree is vacuumized to be better than 4 multiplied by 10 -4 Pa; and after the vacuum degree meets the requirement, opening a gas path valve, introducing argon, setting the gas flow value of the argon to be 70sccm, adjusting a gate valve to enable the working pressure in the vacuum coating chamber to be 0.8Pa, opening a direct-current power switch, and adjusting the autorotation speed of the substrate holder to be 60r/h. And opening the baffle power supply, and cleaning the ion source for 20min. And after the ion source is cleaned, adjusting the flow value of the argon gas back to 70sccm, and adjusting the gate valve to enable the working pressure in the vacuum coating chamber to be 0.8Pa. Regulating the current value of the TiAl alloy target to be 2A, regulating the voltage value to be 396V and sputtering for 115min. Wherein the deposition rate of the TiAl alloy target is 45nm/min. After the deposition is finished, the current of the TiAl alloy target is closed, the argon gas is stopped to be introduced, the gate valve is adjusted to be maximum, when the temperature in the vacuum cavity is reduced to room temperature, the sample is taken out, and Ti is added 3 And obtaining a TiAl single-layer film on the Al alloy.
The TiAl single-layer film obtained in this example was subjected to a high-temperature oxidation test, i.e., ti 3 TiAl single layer film (Ti to be provided with TiAl single layer film) on Al sheet 3 Al sheet) was placed in a crucible,placing the aluminum oxide heat-insulating plug into a tube furnace, placing an aluminum oxide heat-insulating plug at the sealing position, fastening a flange, and sealing the port. And then, turning on a power supply of the mechanical pump, adjusting a temperature rise program of the tube furnace, raising the temperature from room temperature to 800 ℃ at a temperature rise rate of 10 ℃/min, continuously operating the mechanical pump during the temperature rise period, avoiding over severe oxidation caused by overlong temperature rise time, keeping the temperature for one hour after the temperature rises to 800 ℃, turning off the mechanical pump, and simulating the oxidation condition of the mechanical pump in the air. And after the oxidation is finished, closing the power supply of the tube furnace, and cooling the sample to room temperature along with the furnace.
When SEM observation of the cross section and the surface of the TiAl single-layer film after oxidation obtained in this example was performed, as shown in FIG. 3 (b) and FIG. 4 (b), the thickness of the oxide layer was 1.27 μm, and the thickness of the oxide layer was reduced as compared with that of comparative example 1, since continuous and dense Al was formed due to the increase of the Al content 2 O 3 A layer that blocks further diffusion of oxygen. But a large amount of rod-like TiO appears on the surface after oxidation 2 Oxidation products, such as rods, which overgrow to create pores, provide a pathway for oxygen to diffuse inward. Thus, the oxidation resistance of this example is improved over comparative example 1, but the oxidation is still more severe.
The TiAl single-layer film obtained in this example was subjected to hardness test and SEM characterization at indentations, and as shown in fig. 6 (a), its hardness was 8.38GPa; the modulus was 137GPa. From the indentation SEM image (b) in FIG. 6, it was found that the example started to form cracks more significantly, and the crack length was 5 μm. This is caused by the increased brittleness of the film due to the higher Al content.
Example 1
Firstly, ti with phi of 18 x 2mm 3 And sequentially using 1000-mesh, 3000-mesh, 5000-mesh and 7000-mesh sandpaper to polish the Al sheet on a metal polishing machine until the surface is smooth and has no obvious scratch. Ti after polishing treatment 3 Putting the Al sheet in an acetone solvent, performing ultrasonic treatment for 20min, taking out, performing ultrasonic treatment for 20min with ethanol, and drying to obtain clean Ti 3 An Al substrate; fixing the cleaned substrate on a rectangular sample frame, and putting the substrate into a sample chamber of a multi-target magnetron sputtering device; respectively placing the TiAl target and the Cr target in a multi-target magnetron sputtering device, and adjusting the target base distance to be 10cm.
Preparation ofAfter the vacuum is finished, the vacuum cavity is closed, and the vacuum degree is vacuumized to be better than 4 multiplied by 10 -4 Pa; and after the vacuum degree meets the requirement, opening a gas path valve, introducing argon, setting the gas flow value of the argon to be 70sccm, adjusting a gate valve to enable the working pressure in the vacuum coating chamber to be 0.8Pa, opening a direct-current power switch, and adjusting the autorotation speed of the substrate holder to be 60r/h. The shutter power supply was turned on and the ion source was cleaned for 20min. After the ion source is cleaned, the gas flow value of the argon is adjusted back to 70sccm, and the gate valve is adjusted to enable the working pressure in the vacuum coating chamber to be 0.8Pa. Adjusting the current value of the TiAl target to be 2A and the voltage value to be 320V; the Cr target current value is adjusted to be 0.2A, the voltage value is adjusted to be 340V, and the sputtering is carried out for 100min. Wherein the deposition rate of the TiAl target is 45nm/min, and the deposition rate of the Cr target is 5nm/min. After the deposition is finished, the current of the TiAl alloy target and the Cr target is closed, the argon gas is stopped to be introduced, the gate valve is adjusted to be maximum, when the temperature in the vacuum cavity is reduced to room temperature, the sample is taken out, and Ti is added 3 Alternately depositing on the Al sheet to obtain the TiAl/Cr metal nano multilayer film with the modulation ratio of 45:5, as shown in figure 1.
The TiAl/Cr metal nano-multilayer film obtained in this example with a modulation ratio of 45:5 was subjected to a high temperature oxidation experiment, i.e., ti 3 TiAl/Cr metal nano-multilayer film with modulation ratio of 45:5 on Al sheet (Ti with TiAl/Cr metal nano-multilayer film with modulation ratio of 45: 5) 3 Al sheet) was placed in a crucible, which was placed in a tube furnace, a piece of alumina heat-insulating plug was placed at the seal, and the flange was fastened to seal the port. And then, turning on a power supply of the mechanical pump, adjusting a temperature rise program of the tube furnace, raising the temperature from room temperature to 800 ℃ at a temperature rise rate of 10 ℃/min, continuously operating the mechanical pump during the temperature rise period, avoiding over severe oxidation caused by overlong temperature rise time, keeping the temperature for one hour after the temperature rises to 800 ℃, turning off the mechanical pump, and simulating the oxidation condition of the mechanical pump in the air. And after the oxidation is finished, closing the power supply of the tube furnace, and cooling the sample to room temperature along with the furnace.
The sectional and surface SEM observation of the TiAl/Cr metal nano-multilayer film with the modulation ratio of 45:5 obtained in the example was carried out, as shown in (c) in FIG. 3 and (c) in FIG. 4, the thickness of the oxide layer was 575nm, the film structure was relatively loose, and rod-shaped TiO on the surface was present 2 Growth was inhibited and the oxide layer thickness was clear compared to comparative example 2The oxidation resistance of the nano multilayer film is improved by introducing the periodic chromium layer.
The TiAl/Cr metal nano-multilayer film obtained in this example with a modulation ratio of 45:5 was subjected to hardness test and SEM characterization at indentations, as shown in fig. 6 (a), and its hardness was 9.35GPa; the modulus was 150GPa. From the indentation SEM image of (c) in FIG. 6, it was found that the crack of this example was shorter by 2 μm.
Example 2
Firstly, ti with phi of 18 x 2mm 3 The Al sheet is sequentially polished by 1000-mesh, 3000-mesh, 5000-mesh and 7000-mesh sand paper on a metal polishing machine until the surface is smooth and has no obvious scratch. Simultaneously polishing the Ti 3 Putting the Al sheet in an acetone solvent, performing ultrasonic treatment for 20min, taking out, performing ultrasonic treatment for 20min with ethanol, and drying to obtain clean Ti 3 An Al substrate; fixing the cleaned substrate on a rectangular sample rack, and putting the rectangular sample rack into a sample chamber of a multi-target magnetron sputtering device; respectively placing the TiAl target and the Cr target in a multi-target magnetron sputtering device, and adjusting the target base distance to be 10cm. After the preparation is finished, the vacuum cavity is closed, and the vacuum degree is vacuumized to be better than 4 multiplied by 10 -4 Pa; and after the vacuum degree meets the requirement, opening a gas path valve, introducing argon, setting the gas flow value of the argon to be 70sccm, adjusting a gate valve to enable the working pressure in the vacuum coating chamber to be 0.8Pa, opening a direct-current power switch, and adjusting the autorotation speed of the substrate holder to be 60r/h. And opening the baffle power supply, and cleaning the ion source for 20min. And after the ion source is cleaned, adjusting the flow value of the argon gas back to 70sccm, and adjusting the gate valve to enable the working pressure in the vacuum coating chamber to be 0.8Pa. Adjusting the current value of the TiAl alloy target to be 2A and the voltage value to be 320V; the Cr target current value was adjusted to 0.4A, the voltage value was adjusted to 284V, and sputtering was carried out for 77min. Wherein the deposition rate of the TiAl alloy target is 45nm/min, and the deposition rate of the Cr target is 10nm/min. After the deposition is finished, the current of the TiAl target and the Cr target is closed, the argon gas is stopped to be introduced, the gate valve is adjusted to be maximum, when the temperature in the vacuum cavity is reduced to room temperature, the sample is taken out, and Ti is added 3 Alternately depositing on the Al sheet to obtain the TiAl/Cr metal nano multilayer film with the modulation ratio of 45: 10.
The TiAl/Cr metal nano-multilayer film obtained in this example with a modulation ratio of 45:10 was subjected to a high temperature oxidation experiment, i.e., ti 3 TiAl/Cr metal nano-multilayer film with modulation ratio of 45:10 on Al sheet (Ti with TiAl/Cr metal nano-multilayer film with modulation ratio of 45: 10) 3 Al sheet) is placed in a crucible, the crucible is placed in a tube furnace, an aluminum oxide heat insulation plug is placed at the sealing position, a flange is fastened, and the port is sealed. And then, turning on a power supply of the mechanical pump, adjusting a temperature rise program of the tube furnace, raising the temperature from room temperature to 800 ℃ at a temperature rise rate of 10 ℃/min, continuously operating the mechanical pump during the temperature rise period, avoiding excessively severe oxidation caused by overlong temperature rise time, keeping the temperature for one hour after the temperature is raised to 800 ℃, turning off the mechanical pump, and simulating the oxidation condition of the mechanical pump in the air. And after the oxidation is finished, closing the power supply of the tube furnace, and cooling the sample to room temperature along with the furnace.
When the sectional and surface SEM observations of the TiAl/Cr metal nano-multilayer film obtained in this example with a modulation ratio of 45:10 were made, as shown in FIG. 3 (d) and FIG. 4 (d), the thickness of the oxide layer was 224nm, the outer layer of the film was affected by oxygen more loosely, but the inner layer of the film was still denser. Oxidation of surface rod-like grown TiO 2 Almost disappeared and the surface pores are less, indicating that the oxidation resistance is further improved. Subsequently, a sectional TEM observation was made of the TiAl/Cr metal nano-multilayer film obtained in this example with a modulation ratio of 45:10, as shown in FIG. 5. The thickness of the oxide layer is about 300nm, obvious layering phenomenon appears, ti and Al elements are separated and rearranged under the preferential oxidation induction of the chromium layer, and aluminum elements are preferentially formed with the chromium elements (Cr, al) 2 O 3 A ternary compact oxide layer to form a multi-layer oxide layer barrier and avoid TiO 2 And Al 2 O 3 The mixture appears, the TiO growing in a rod shape 2 The nano oxide layer is confined to prevent oxygen from further diffusing inwards, and the oxidation resistance is improved to a certain degree.
The TiAl/Cr metal multilayer nano-film obtained in this example with a modulation ratio of 45:10 was subjected to hardness test and SEM characterization at indentations, as shown in fig. 6 (a), and its hardness was 10GPa; the modulus is 165Gpa, which is superior to TiAl single-layer film. From the indentation SEM image of fig. 6 (d), it was found that cracks were hardly observed in this example, indicating that both the hardness and toughness of the TiAl/Cr metal nano-multilayer film were improved as compared with the TiAl single-layer film.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (9)

1. Is suitable for Ti 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection comprises a modulation unit formed by a plurality of component-alternating metal sublayers, and is characterized in that: the modulation unit comprises a TiAl sublayer and a Cr sublayer, wherein the TiAl sublayer and the Cr sublayer are metal sublayers.
2. A Ti alloy according to claim 1 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection is characterized in that: number of the modulation units>1, and when the number of the modulation units>1, the modulation units are arranged in a superposition mode.
3. A Ti alloy as defined in claim 1 suitable for use in a Ti alloy 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection is characterized in that: the thickness of the TiAl/Cr nano multilayer film is 4-5 mu m.
4. A Ti alloy according to claim 1 3 The high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection is characterized in that: the thickness of the TiAl sublayer is 30-60 nm; the thickness of the Cr sublayer is 1-50 nm.
5. A Ti alloy according to claim 1 3 The preparation method of the high-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection is characterized by comprising the following steps of:
s1: placing the substrate on a sample frame, placing the sample frame into a film coating chamber of a magnetron sputtering device, mounting a TiAl target and a Cr target on a target position of the sputtering device, and vacuumizing a cavity;
s2: and opening the substrate to rotate, introducing argon, starting magnetron sputtering, and obtaining the TiAl/Cr metal nano multilayer film on the surface of the substrate after sputtering is finished.
6. A Ti alloy according to claim 5 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection is characterized by comprising the following steps: in the above S1, the substrate is washed and dried in this order before use; the cleaning is ultrasonic cleaning in acetone and ethanol in sequence.
7. A Ti alloy according to claim 5 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection is characterized by comprising the following steps: in the step S2, in the sputtering process, the substrate surface is parallel to the sputtering target surface, and the TiAl target and the Cr target are mounted on the corresponding target positions of the multi-target magnetron sputtering coating chamber, so that the substrate and the target surface are parallel.
8. A Ti alloy according to claim 5 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection is characterized by comprising the following steps: in the S2, the sputtering current of the TiAl target is 1-3A; the sputtering current of the Cr target is 0.1-3A.
9. A Ti alloy according to claim 5 3 The preparation method of the high-temperature oxidation resistant TiAl/Cr nano multilayer coating for Al protection is characterized by comprising the following steps: in the above S2, the substrate rotation rate is preferably 30 to 90r/h.
CN202210691349.9A 2022-06-17 2022-06-17 Is suitable for Ti 3 High-temperature oxidation-resistant TiAl/Cr nano multilayer coating for Al protection and preparation method and application thereof Pending CN115142017A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020009383A1 (en) * 1996-03-29 2002-01-24 Hiroyuki Kawaura Tial-based alloys with excellent oxidation resistance. and method for producing the same
CN104553139A (en) * 2014-07-11 2015-04-29 陶冶 Metal-ceramic composite structure type multilayer nano film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020009383A1 (en) * 1996-03-29 2002-01-24 Hiroyuki Kawaura Tial-based alloys with excellent oxidation resistance. and method for producing the same
CN104553139A (en) * 2014-07-11 2015-04-29 陶冶 Metal-ceramic composite structure type multilayer nano film and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
席艳君等: "TiAl涂层对Ti_3Al合金腐蚀行为的影响", 《材料工程》 *

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