WO2022062102A1

WO2022062102A1 - Diffusion-resistant high-entropy alloy coating material, heat resistant coating material, preparation method therefor, and application thereof

Info

Publication number: WO2022062102A1
Application number: PCT/CN2020/127792
Authority: WO
Inventors: 汪唯; 许中湛; 王磊; 洪悦; 石倩; 林松盛; 郭朝乾; 唐鹏; 苏一凡; 代明江; 王红莉; 唐春梅
Original assignee: 广东省科学院新材料研究所
Priority date: 2020-09-23
Filing date: 2020-11-10
Publication date: 2022-03-31
Also published as: CN112064024A; CN112064024B

Abstract

A diffusion-resistant high-entropy alloy coating material and a heat resistant coating material, comprising a substrate and a diffusion-resistant high-entropy alloy coating. The diffusion-resistant high-entropy alloy coating comprises the elements: Al, Co, Cr, Ni, and Mo. The heat resistant coating material is obtained by forming the aforementioned diffusion-resistant high-entropy alloy coating on the substrate, and then, using same as a base material, forming a heat resistant coating thereon. By utilizing a unique slow diffusion effect of the diffusion-resistant high-entropy alloy coating and good physical and chemical matching thereof with both the substrate and the heat resistant coating, it is possible to effectively inhibit mutual diffusion of alloy components and harmful phase precipitation at the contact surface between the substrate and the coating, and improve the high temperature oxidation resistance capability of the coating. The heat resistant coating material can be applied in the preparation of hot-end parts of aeronautical engines or gas turbines to improve the service life and working reliability of the parts.

Description

Diffusion resistance high entropy alloy coating material, high temperature resistant coating material and preparation method and application thereof

CROSS-REFERENCE TO RELATED APPLICATIONS

This application requires the priority of the Chinese patent application with the application number 202011005908.3 and the title of "Diffusion-resistant high-entropy alloy coating material, high temperature resistant coating material and preparation method and application thereof" submitted to the China Patent Office on September 23, 2020 rights, the entire contents of which are incorporated herein by reference.

technical field

The present disclosure relates to the technical field of coating preparation, and in particular, to diffusion-resistant high-entropy alloy coating materials, high-temperature resistant coating materials, and preparation methods and applications thereof.

Background technique

The service environment of aero-engine or gas turbine turbine blades is harsh, and its working temperature is extremely high, which has far exceeded the extreme temperature that superalloy materials can withstand. However, due to the large difference in composition between the coating material and the superalloy substrate, element interdiffusion will inevitably occur between the coating and the alloy substrate during high temperature service. Among them, the main anti-oxidant element Al of the coating diffuses into the substrate, which will accelerate the consumption of Al element and reduce the service life of the blade; while the solid solution strengthening elements Mo, Re, Cr, W, etc. of the substrate material are in the direction of the coating. Outdiffusion, it is easy to form some intermetallic compound phases and topologically densely packed phases at the interface, which significantly reduces the mechanical properties of the base alloy. Therefore, the interdiffusion between the coating and the superalloy substrate has become a key problem that restricts the performance of the alloy and coating, and will seriously affect the service life and working reliability of turbine blades.

In order to solve the reduction of coating life and the degradation of substrate mechanical properties caused by interdiffusion, a lot of research work has been carried out at home and abroad, mainly focusing on preventing recrystallization, improving coating structure and activity, and interfacial diffusion resistance. Among them, diffusion barrier is considered to be one of the most direct and effective methods. It usually adds a barrier layer (ie diffusion barrier) between the coating and the substrate to block the interdiffusion between elements.

At present, the diffusion barrier materials are mainly metals (precious metals or refractory metals) and ceramics, but the metal diffusion barrier has the problem of poor chemical matching with the coating/substrate, and its blocking effect is not good when multiple elements are interdiffused at the same time. However, the ceramic layer diffusion barrier has the problem of poor physical matching with the substrate, and is prone to thermal shock failure. It can be seen that the good physical and chemical matching between the diffusion barrier and the substrate is the key problem to be solved urgently in the current diffusion barrier research process.

In view of this, the present disclosure is hereby made.

SUMMARY OF THE INVENTION

Embodiments of the present disclosure propose a diffusion-resistant high-entropy alloy coating material, which includes a substrate and a diffusion-resistant high-entropy alloy coating, and elements of the diffusion-resistant high-entropy alloy coating include Al, Co, Cr, Ni, and Mo.

Optionally, in atomic percent, the elements of the diffusion barrier high-entropy alloy coating include Al 15%-30%, Co 15%-30%, Cr 15%-30%, Ni 15%-30% and Mo 15%-30%.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 1:1:1:1:1 by atomic percentage.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 1.1:1.1:1.1:1.1:0.6 in atomic percentage.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 1.1:1.1:1:1:0.8 in atomic percentage.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 1:1.5:0.75:1:0.75 in atomic percentage.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 0.9:0.9:1:1:1.2 in atomic percentage.

Optionally, the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 0.8:1.1:0.9:1.2:1 by atomic percentage.

Optionally, the base material is a superalloy.

Optionally, the base material is an iron-based superalloy, a nickel-based superalloy or a cobalt-based superalloy.

Embodiments of the present disclosure also provide a preparation method for preparing a diffusion-resistant high-entropy alloy coating material, including: forming a diffusion-resistant high-entropy alloy coating on the surface of the substrate.

Optionally, the forming of the diffusion-resistant high-entropy alloy coating on the surface of the substrate includes preparing Al, Co, Cr, Ni and Mo into a single alloy target, and then magnetron sputtering the single alloy target. The diffusion-resistant high-entropy alloy coating is formed on the surface of the substrate by means of radiation or arc ion plating.

Optionally, the single alloy target is prepared by smelting or powder metallurgy.

Optionally, the thickness of the diffusion-resistant high-entropy alloy coating is 2 μm-8 μm, preferably 2 μm-7 μm, more preferably 2 μm-6 μm, more preferably 2 μm-5 μm, and more preferably 2 μm-4 μm.

Optionally, when the diffusion-resistant high-entropy alloy coating is formed by means of magnetron sputtering, it is performed under the conditions that the background vacuum degree is less than or equal to 5×10 ^-3 Pa and the substrate temperature is 100-300°C; Preferably, the target power is 200-300W, the DC bias of the substrate is -100--500V, the duty cycle is 60-90%, the target-base distance is 10-15cm, the working argon gas pressure is 0.6-0.8Pa, and the ion source is 0.8 -1.2A.

Optionally, when forming the diffusion-resistant high-entropy alloy coating by means of arc ion plating, it is performed under the conditions that the background vacuum degree is less than or equal to 5×10 ^-3 Pa and the substrate temperature is 200-400°C; preferably ground, the target current is 70-90A, the substrate DC bias is -100--500V, the duty cycle is 60-90%, the target-base distance is 20-30cm, the working argon gas pressure is 1-1.3Pa, and the permanent magnet strength is 1500- 2000Gs, solenoid voltage 20-30V.

Optionally, before forming the diffusion-resistant high-entropy alloy coating on the surface of the substrate, the preparation method of the diffusion-resistant high-entropy alloy coating material further comprises: pre-processing the substrate, the pre-treatment The treatment includes grinding and polishing the surface of the substrate, then ultrasonic cleaning with acetone, alcohol and deionized water, respectively, and drying.

Embodiments of the present disclosure also provide a high temperature resistant coating material, comprising a material body and a high temperature resistant coating applied on the material body, wherein the material body is the above-mentioned diffusion-resistant high-entropy alloy coating material or the above-mentioned diffusion-resistant high-entropy alloy coating material. The anti-diffusion high-entropy alloy coating material obtained by the preparation method of the entropy alloy coating material.

Optionally, the high temperature resistant coating is PtAl coating, NiAl coating, NiAlHf coating, NiCrAlY coating, CoCrAlY coating, NiAlPtNb coating, NiAlHfRu coating, CoCrAlYSi coating, NiCoCrAlYTa coating, NiCrAlYLaB coating , any one of NiCoCrAlYHf coating and NiCoCrAlYTaRe coating.

Embodiments of the present disclosure also provide a method for preparing a high temperature resistant coating material, which includes preparing a high temperature resistant coating on the surface of the material body.

Optionally, the method for preparing the high temperature resistant coating is selected from magnetron sputtering, electron beam physical vapor deposition, arc ion plating, flame spraying, atmospheric plasma spraying, vacuum plasma spraying, cold spraying, plasma spraying-physical vapor deposition and at least one of pulse plating.

The embodiments of the present disclosure also propose the application of the above-mentioned high-temperature resistant coating material or the high-temperature resistant coating material obtained by the above-mentioned preparation method of the above-mentioned high temperature resistant coating material in the preparation of aero-engine or gas turbine hot-end components.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present disclosure more clearly, the following briefly introduces the accompanying drawings that need to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present disclosure, and therefore do not It should be regarded as a limitation of the scope, and for those of ordinary skill in the art, other related drawings can also be obtained according to these drawings without any creative effort.

Fig. 1 is AlCoCrNiMo high-entropy alloy coating scanning electron microscope (SEM) cross-sectional topography and X-ray diffraction pattern in this embodiment;

Figure 2 shows the cross-sectional morphologies of the high-temperature coating (NiAlHf)/diffusion barrier (AlCoCrNiMo)/superalloy (N5) sample in the example after being oxidized at 1100°C for 0h and 50h;

Figure 3 shows the cross-sectional morphologies of the NiAlHf/N5 sample in the comparative example after being oxidized at 1100 °C for 0 h and 50 h;

Fig. 4 is the oxidation weight gain curve of NiAlHf/AlCoCrNiMo/N5 sample (NCN) and NiAlHf/N5 sample (NN) under the condition of 1100 ℃ in the embodiment;

Figure 5 shows the cross-sectional morphologies of the NiAlHf/AlTiCrNiMo/N5 samples in the comparative example after being oxidized at 1100 °C for 0 h and 50 h.

detailed description

In order to make the objectives, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions in the embodiments of the present disclosure will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The beneficial effects of the diffusion-resistant high-entropy alloy coating material and the preparation method thereof provided by the embodiments of the present disclosure are: the diffusion-resistant high-entropy alloy coating is formed by using Al, Co, Cr, Ni, and Mo, and the diffusion-resistant high-entropy alloy coating is formed by using Al, Co, Cr, Ni and Mo. The coating has good physical and chemical matching with the substrate and other coatings (such as high temperature coatings), which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high temperature resistance of the coating. Oxidation ability, and at the same time avoid mutual diffusion to reduce the mechanical properties of the substrate, prolong the service life of the parts, and its diffusion resistance effect is significantly improved compared with traditional metal or ceramic diffusion resistance materials.

The embodiments of the present disclosure also provide a high temperature resistant coating material and a preparation method thereof. By forming the above-mentioned anti-diffusion high-entropy alloy coating on a substrate, and then using this as a material body to form a high-temperature resistant coating, using the high-entropy anti-diffusion alloy coating The alloy coating has a unique slow diffusion effect, and has good physical and chemical matching with the substrate and the high temperature resistant coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, improve the coating performance. high temperature oxidation resistance. The high temperature resistant coating material can be used in the preparation of aero-engine or gas turbine hot-end components, so as to improve the service life and working reliability of the components.

The following will specifically describe the diffusion-resistant high-entropy alloy coating materials, the high-temperature resistant coating materials, and the preparation methods and applications thereof provided by the embodiments of the present disclosure.

Embodiments of the present disclosure provide a method for preparing a high temperature resistant coating material, which comprises first forming a diffusion-resistant high-entropy alloy coating on a substrate, and using this as a material body to form a high temperature resistant coating thereon, so as to obtain a High temperature resistant coating material. details as follows:

S1. Preparation of diffusion-resistant high-entropy alloy coating materials

A diffusion-resistant high-entropy alloy coating is formed on the surface of the substrate, and the elements of the diffusion-resistant high-entropy alloy coating include Al, Co, Cr, Ni and Mo. The present disclosure finds that the diffusion-resistant high-entropy alloy coating formed by the above five elements can effectively inhibit the interdiffusion of alloy components and the precipitation of harmful phases at the interface between the substrate and other coatings (especially high-temperature coatings), and improve the high-temperature resistance of the coating. Oxidation ability, while avoiding interdiffusion to reduce the mechanical properties of the substrate and prolong the service life of the parts. If the elements are replaced, such as replacing Co with Ti, such a good diffusion resistance effect cannot be achieved at all.

Further, in atomic percent, the elements of the diffusion-resistant high-entropy alloy coating include Al 15%-30%, Co 15%-30%, Cr 15%-30%, Ni 15%-30% and Mo 15%- 30%. The amount of elements in the high-entropy alloy is about the same amount. The inventors of the present disclosure further control the amount of each component, so that the formation of the diffusion-resistant high-entropy alloy coating can be a single-phase solid solution or an amorphous phase structure to ensure the diffusion barrier composition. The structure is uniform, and there is no component segregation or precipitation phase, which is beneficial to the diffusion resistance of elements. For example, a single alloy target can be prepared by smelting or powder metallurgy after uniformly mixing Al, Co, Cr, Ni and Mo metal powders at a ratio of 1:1:1:1:1 atomic percentage; Al, Co, Cr, Ni and Mo metal powders are uniformly mixed in a ratio of 1.1:1.1:1.1:1.1:0.6 atomic percentage, and then a single alloy target is prepared by smelting or powder metallurgy; Al, Co, Cr can be selected , Ni and Mo metal powders are uniformly mixed in a ratio of 1.1:1.1:1:1:0.8 atomic percentage, and then a single alloy target is prepared by smelting or powder metallurgy; Al, Co, Cr, Ni and Mo metal powders can be selected. A single alloy target is prepared by smelting or powder metallurgy after uniform mixing in the ratio of atomic percentage of 1:1.5:0.75:1:0.75; Al, Co, Cr, Ni and Mo metal powders can be selected in atomic percentage of 0.9: A single alloy target is prepared by smelting or powder metallurgy after uniform mixing in a ratio of 0.9:1:1:1.2; or Al, Co, Cr, Ni and Mo metal powders can be selected in an atomic percentage of 0.8:1.1:0.9:1.2 A single alloy target is prepared by smelting or powder metallurgy after uniform mixing in the ratio of : 1.

Specifically, Al, Co, Cr, Ni and Mo are prepared into a single alloy target, and then the single alloy target is formed on the surface of the substrate by means of magnetron sputtering or arc ion plating to form a diffusion-resistant high-entropy alloy coating. The specific process of magnetron sputtering or arc ion plating can refer to the existing process steps, wherein the high-entropy alloy coating with uniform composition and structure formed by the method of magnetron sputtering has more excellent diffusion resistance performance.

Specifically, the base material is a superalloy, such as a common superalloy material such as iron-based superalloy, nickel-based superalloy, or cobalt-based superalloy, which is not limited in the embodiments of the present disclosure. The thickness of the diffusion barrier high entropy alloy coating is 2 μm-8 μm, preferably 2 μm-7 μm, more preferably 2 μm-6 μm, more preferably 2 μm-5 μm, and more preferably 2 μm-4 μm. In the art, generally, the thicker the diffusion-resistant high-entropy alloy coating, the better its diffusion-resistant performance, but the thicker the coating, the heavier the coating will be. In the present application, this thickness range can not only effectively suppress the interdiffusion of alloy components between the substrate and the high-temperature coating, but also ensure the applicability of the high-entropy alloy diffusion barrier layer (that is, realize the thin coating and Good diffusion resistance performance can be achieved, and the deposition time of the thin coating is not too long, and the influence on the weight gain of the component is small, that is, the effect of small weight gain is guaranteed). Of course, in other embodiments of the present disclosure, the thickness of the coating layer can also be adjusted according to requirements, which is not limited by the embodiments of the present disclosure.

When magnetron sputtering is used to form a diffusion-resistant high-entropy alloy coating, the specific parameters are as follows: the background vacuum is less than or equal to 5×10 ^-3 Pa, the substrate temperature is 100-300°C, the target power is 200-300W, and the substrate temperature is 200-300W. The DC bias voltage is -100--500V, the duty ratio is 60-90%, the target-base distance is 10-15cm, the working argon gas pressure is 0.6-0.8Pa, and the ion source is 0.8-1.2A.

When arc ion plating is used to form a diffusion-resistant high-entropy alloy coating, the specific parameters are as follows: the background vacuum is less than or equal to 5×10 ^-3 Pa, the substrate temperature is 200-400°C, the target current is 70-90A, the substrate DC The bias voltage is -100--500V, the duty ratio is 60-90%, the target base distance is 20-30cm, the working argon gas pressure is 1-1.3Pa, the permanent magnet strength is 1500-2000Gs, and the electromagnetic coil voltage is 20-30V.

It should be noted that by further optimizing the process parameters of magnetron sputtering and arc ion plating, the formed coating has a dense structure, uniform composition and better high temperature oxidation resistance. By preparing the high-entropy alloy coating within the above parameter range, the comprehensive performance of the coating and the diffusion resistance effect can be effectively guaranteed. Of course, in other embodiments of the present disclosure, process parameters may also be adjusted according to requirements, which are not limited in the embodiments of the present disclosure.

S2, the formation of high temperature resistant coating

A high-temperature resistant coating is prepared on the surface of the material body by using the diffusion-resistant high-entropy alloy coating material as the material body. The formed high-temperature resistant coating material utilizes the slow diffusion effect unique to the diffusion-resistant high-entropy alloy coating, and has good physical and chemical matching with the substrate and the high-temperature resistant coating, which can effectively inhibit the substrate and the coating. The interdiffusion of interlayer alloy components and the precipitation of harmful phases at the interface improve the high temperature oxidation resistance of the coating. It can be used in the preparation of aero-engine or gas turbine hot-end components to improve the service life and working reliability of components.

Specifically, the high temperature resistant coatings are PtAl coating, NiAl coating, NiAlHf coating, NiCrAlY coating, CoCrAlY coating, NiAlPtNb coating, NiAlHfRu coating, CoCrAlYSi coating, NiCoCrAlYTa coating, NiCrAlYLaB coating, NiCoCrAlYHf coating layer and NiCoCrAlYTaRe coating. The above coating materials are all existing high temperature resistant coatings, which are suitable for the high temperature resistant coatings of the high temperature resistant coating materials provided in the embodiments of the present disclosure, and have good physical and chemical compatibility.

Specifically, the method for preparing the high temperature resistant coating is selected from magnetron sputtering, electron beam physical vapor deposition, arc ion plating, flame spraying, atmospheric plasma spraying, vacuum plasma spraying, cold spraying, plasma spraying-physical vapor deposition and pulse electroplating at least one of them. It can be a common coating formation method such as supersonic flame spraying, low-pressure plasma spraying, etc. The specific process can refer to the prior art records, and will not be repeated here.

The features and properties of the present disclosure will be further described in detail below with reference to the embodiments.

Example 1

The present embodiment provides a preparation method of a high temperature resistant coating material, which is prepared by the following methods:

(1) Target preparation: Al, Co, Cr, Ni and Mo metal powders are uniformly mixed in a ratio of 1:1:1:1:1 atomic percentage, and a single alloy is prepared by powder metallurgy as a target.

(2) Substrate pretreatment: Using nickel-based superalloy (N5) as the substrate, the surface of the substrate was ground and polished, and then ultrasonically cleaned with acetone, alcohol and deionized water, respectively, and dried.

(3) Diffusion-resistant high-entropy alloy coating deposition: use magnetron sputtering to deposit the target material on the surface of the substrate after cleaning and blowing to form a diffusion-resistant high-entropy alloy coating, and the process parameters are: the background vacuum degree is less than 5×10 ^-3 Pa, substrate temperature of 200°C, target power of 250W, substrate DC bias of -100V, duty cycle of 70%, target-to-substrate distance of 12cm, working argon pressure of 0.7Pa, and ion source of 1A. The thickness of the control coating is about 3 μm.

(4) Deposition of high temperature resistant coating: Arc ion plating is used to deposit NiAlHf high temperature resistant coating with a thickness of about 30 μm on the surface of the diffusion resistance high entropy alloy coating. The process parameters are: the background vacuum is less than 5×10 ^-3 Pa, the base The material temperature is 350°C, the argon gas pressure is 2Pa, the arc current is 120A, the DC bias voltage is -100V, and the duty ratio is 70%. The chemical composition of the NiAlHf coating is as follows: the Ni content is 68 wt.%, the Al content is 31 wt.%, and the Hf content is 1 wt.%. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 2

This embodiment provides a method for preparing a high temperature resistant coating material, which is different from Embodiment 1 only in that: in step (3), the magnetron sputtering process parameters for the deposition of the diffusion-resistant high-entropy alloy coating are: background The vacuum degree is less than 5×10 ^-3 Pa, the substrate temperature is 150°C, the target power is 300W, the substrate DC bias is -300V, the duty cycle is 90%, the target-base distance is 10cm, the working argon gas pressure is 0.8Pa, the ion source is 1.2A. The control coating thickness was 4 μm. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 3

This embodiment provides a method for preparing a high temperature resistant coating material, which is different from Embodiment 1 only in that: in step (3), the magnetron sputtering process parameters for the deposition of the diffusion-resistant high-entropy alloy coating are: background The vacuum degree is less than 5×10 ^-3 Pa, the substrate temperature is 250°C, the target power is 250W, the substrate DC bias is -500V, the duty cycle is 60%, the target-base distance is 15cm, the working argon gas pressure is 0.6Pa, the ion source is 0.8A. The control coating thickness was 2 μm. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 4

The present embodiment provides a method for preparing a high temperature resistant coating material, which differs from Embodiment 1 only in that: in step (3), the arc ion plating technology is used for the deposition of the diffusion-resistant high-entropy alloy coating, and the process parameters are: The background vacuum is less than 5×10 ^- ³ Pa, the substrate temperature is 300°C, the target current is 70A, the substrate pulse bias is -100V, the duty cycle is 70%, the target-to-base distance is 20cm, and the working argon gas pressure is 1.3 Pa, permanent magnet strength 2000Gs, electromagnetic coil voltage 30V. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 5

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from Embodiment 1 only in that in step (3), arc ion plating technology is used for coating deposition, and the process parameters are: the background vacuum degree is less than 5 ×10 ^-3 Pa, substrate temperature is 350℃, target current is 90A, substrate pulse bias is -300V, duty cycle is 90%, target-base distance is 30cm, working argon gas pressure is 1Pa, permanent magnet strength is 1500Gs , the solenoid voltage is 25V. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 6

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from the embodiment 1 only in that in step (1), the atomic percentages of the Al, Co, Cr, Ni, and Mo metal powders used are: 1.1:1.1:1.1:1.1:0.6. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 7

This embodiment provides a preparation method of a high temperature resistant coating material, the difference between which is different from that in Embodiment 1 is only that in step (2), the base material used is a cobalt-based superalloy (GH605). The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 8

This embodiment provides a method for preparing a high temperature resistant coating material, which is different from Embodiment 1 only in that in step (2), the substrate material used is an iron-based superalloy (GH706). The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 9

This embodiment provides a method for preparing a high temperature resistant coating material, which is different from Embodiment 1 only in that in step (4), magnetron sputtering is used to deposit a thickness of about 20 μm on the surface of the diffusion resistance high entropy alloy coating. The process parameters of the CoCrAlY anti-high temperature coating are as follows: the background vacuum is less than 5×10 ^-3 Pa, the substrate temperature is 150°C, the argon pressure is 0.4Pa, the target current is 2.5A, the bias voltage is -100V, and the ion source is 1.5A. The chemical composition of CoCrAlY coating is: Cr content is 40wt.%, Al content is 15wt.%, Y content is 3wt.%, and the rest is Co. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 10

This embodiment provides a method for preparing a high temperature resistant coating material, which differs from Example 1 only in that: in step (4), a CoCrAlYSi high temperature resistant coating of about 40 μm is prepared by supersonic flame spraying, and the process parameters are: : Spray gun power 3kW, gas flow rate: 50m3/h, powder feeding amount: 5g/min, spraying distance: 300mm. The chemical composition of CoCrAlYSi coating is: Cr content is 18wt.%, Al content is 12wt.%, Y content is 3wt.%, Si content is 1.5wt.%, and the rest is Ni. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 11

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from the embodiment 1 only in that in step (1), the atomic percentages of the Al, Co, Cr, Ni, and Mo metal powders used are: 1.1:1.1:1:1:0.8. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 12

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from the embodiment 1 only in that in step (1), the atomic percentages of the Al, Co, Cr, Ni, and Mo metal powders used are: 1:1.5:0.75:1:0.75. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 13

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from the embodiment 1 only in that in step (1), the atomic percentages of the Al, Co, Cr, Ni, and Mo metal powders used are: 0.9:0.9:1:1:1.2. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Example 14

The present embodiment provides a method for preparing a high temperature resistant coating material, which is different from the embodiment 1 only in that in step (1), the atomic percentages of the Al, Co, Cr, Ni, and Mo metal powders used are: 0.8:1.1:0.9:1.2:1. The obtained high-temperature resistant coating material utilizes the unique resistance-diffusion effect of the resistance-diffusion high-entropy alloy coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high-temperature oxidation resistance of the coating.

Comparative Example 1

This comparative example provides a preparation method of a high temperature resistant coating material, which differs from Example 1 only in that the NiAlHf high temperature resistant coating is directly formed on the nickel-based superalloy without depositing the diffusion-resistant high-entropy alloy coating.

Comparative Example 2

The present comparative example provides a preparation method of a high temperature resistant coating material, which is different from Example 1 only in that Co metal powder is replaced with Ti metal powder.

Test Example 1

Structural characterization of the diffusion-resistant high-entropy alloy coating formed during the preparation of the high temperature resistant coating material in Example 1, including scanning electron microscopy and XRD detection, the results are shown in Figure 1 (a) and Figure 1 (b) ; The phase structure of the diffusion-resistant high-entropy alloy coating obtained in Example 2 was detected by XRD, as shown in (c) in Figure 1 .

The SEM image of the cross-section of the diffusion resistance high-entropy alloy coating is shown in Figure 1 (a), the coating structure is dense and the composition is uniform, and its phase structure is detected by XRD, as shown in Figure 1 (b), the coating is non- crystal phase. As shown in Fig. 1(c), the coating is a single solid solution phase (FCC structure).

Test Example 2

The high temperature interface element diffusion behavior of the high temperature resistant coating materials prepared in Example 1 and Comparative Example 1 was tested, and the high temperature coating (NiAlHf)/diffusion barrier (AlCoCrNiMo)/superalloy ( N5) The sample was subjected to an oxidation test at 1100°C. The cross-sectional backscattered images of the sample after 50 hours are shown in Figures 2 and 3. Figure 2 shows the test results in Example 1, and Figure 3 shows the results in Comparative Example 1. Test Results.

The results in Fig. 2 show that after 50 hours of oxidation at 1100 °C, no obvious interdiffusion zone and secondary reaction zone were observed in the NiAlHf/AlCoCrNiMo/N5 coating sample, and no TCP harmful phase was precipitated. This shows that the AlCoCrNiMo high-entropy alloy coating can effectively prevent the interdiffusion of alloy elements and inhibit the precipitation of harmful phases caused by interdiffusion.

Figure 3 shows that after 50 hours of oxidation at 1100 °C, the NiAlHf/N5 coating sample has an obvious element interdiffusion zone, a secondary reaction zone (SRZ) is formed under the interdiffusion layer, and a large number of needle-like TCP harmful phases are precipitated .

The oxidation weight gain curves of the high temperature resistant coating materials prepared in Test Example 1 and Comparative Example 1 are shown in FIG. 4 , where NCN is the test result of Example 1, and NN is the test result of Comparative Example 1. It can be shown that the preparation method provided in this application can effectively form the AlCoCrNiMo high-entropy alloy diffusion barrier layer, realize the barrier diffusion between the high temperature protective coating and the high temperature substrate, and improve the high temperature oxidation resistance of the coating.

Test Example 3

The high temperature interface element diffusion behavior of the high temperature resistant coating materials prepared in Example 1 and Comparative Example 2 was tested, and the high temperature coating (NiAlHf)/diffusion barrier (AlCoCrNiMo)/superalloy ( The N5) sample and the high temperature coating (NiAlHf)/diffusion barrier (AlTiCrNiMo)/superalloy (N5) sample were subjected to oxidation test at 1100 ℃. , FIG. 2 is the test result in Example 1, and FIG. 5 is the test result in Comparative Example 2.

The results in Figure 5 show that after 50 hours of oxidation at 1100 °C, the NiAlHf/AlTiCrNiMo/N5 coating sample has obvious interdiffusion zone and secondary reaction zone, and a large number of TCP harmful phases are precipitated, indicating that compared with Example 1, Comparative Example 2 The AlTiCrNiMo high-entropy alloy coating in the medium has no obvious diffusion resistance effect.

In summary, the present disclosure provides a diffusion-resistant high-entropy alloy coating material and a preparation method thereof, which form a diffusion-resistant high-entropy alloy coating by using Al, Co, Cr, Ni and Mo, and the diffusion-resistant high-entropy alloy coating is The alloy coating has good physical and chemical matching with the substrate and other coatings (such as high-temperature coatings), which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the resistance of the coating. High temperature oxidation ability, while avoiding mutual diffusion to reduce the mechanical properties of the substrate, prolonging the service life of the parts, its diffusion resistance effect is significantly improved compared to traditional metal or ceramic diffusion resistance materials.

The present disclosure also provides a high-temperature resistant coating material and a preparation method thereof. By forming the above-mentioned resistance-diffusion high-entropy alloy coating on a substrate, and then using this as the material body to form a high-temperature resistant coating, the resistance-diffusion high-entropy alloy coating is formed by using the resistance-diffusion high-entropy alloy coating. The alloy coating has a unique slow diffusion effect, and has good physical and chemical matching with the substrate and the high temperature resistant coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, improve the coating performance. high temperature oxidation resistance. The method is mature and reliable, has good repeatability, and is easy to realize large-scale industrial production.

The high temperature resistant coating material can be used in the preparation of aero-engine or gas turbine hot-end components, so as to improve the service life and working reliability of the components.

The embodiments described above are some, but not all, embodiments of the present disclosure. The detailed descriptions of the embodiments of the present disclosure are not intended to limit the scope of the disclosure as claimed, but are merely representative of selected embodiments of the disclosure. Based on the embodiments in the present disclosure, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present disclosure.

Industrial Applicability

The multi-resistance-diffusion high-entropy alloy coating material and the preparation method thereof of the present disclosure are formed by using Al, Co, Cr, Ni and Mo to form the resistance-diffusion high-entropy alloy coating, the resistance-diffusion high-entropy alloy coating and the substrate and Other coatings (such as high temperature coatings) have good physical and chemical matching, which can effectively inhibit the mutual diffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, improve the high temperature oxidation resistance of the coating, and avoid mutual diffusion. Diffusion leads to a decrease in the mechanical properties of the substrate and prolongs the service life of the parts. Compared with traditional metal or ceramic anti-diffusion materials, its diffusion resistance effect is significantly improved. The high-temperature resistant coating material and the preparation method thereof of the present disclosure are formed by forming the above-mentioned anti-diffusion high-entropy alloy coating on the base material, and then using the high-entropy alloy coating as the material body to form the high-temperature resistant coating, using the unique properties of the anti-diffusion high entropy alloy coating It has slow diffusion effect, and has good physical and chemical matching with the substrate and high temperature resistant coating, which can effectively inhibit the interdiffusion of alloy components between the substrate and the coating and the precipitation of harmful phases at the interface, and improve the high temperature oxidation resistance of the coating. . The high temperature resistant coating material can be used in the preparation of aero-engine or gas turbine hot-end components, so as to improve the service life and working reliability of the components.

Claims

A diffusion-resistant high-entropy alloy coating material is characterized in that it comprises a base material and a diffusion-resistant high-entropy alloy coating, and the elements of the diffusion-resistant high-entropy alloy coating include Al, Co, Cr, Ni and Mo.
The diffusion-resistant high-entropy alloy coating material according to claim 1, wherein, in atomic percent, the elements of the diffusion-resistant high-entropy alloy coating include Al 15%-30%, Co 15%-30% , Cr 15%-30%, Ni 15%-30% and Mo 15%-30%.
The diffusion-resistant high-entropy alloy coating material according to claim 1 or 2, wherein the Al, Co, Cr, Ni and Mo of the diffusion-resistant high-entropy alloy coating are in a ratio of 1:1 by atomic percentage: 1:1:1.
The barrier-diffusion high-entropy alloy coating material of claim 1 or 2, wherein the ratio of Al, Co, Cr, Ni and Mo in the barrier-diffusion high-entropy alloy coating is 1.1:1.1: 1.1:1.1:0.6.
The barrier-diffusion high-entropy alloy coating material of claim 1 or 2, wherein the ratio of Al, Co, Cr, Ni and Mo in the barrier-diffusion high-entropy alloy coating is 1.1:1.1: 1:1:0.8.
The diffusion-resistant high-entropy alloy coating material of claim 1 or 2, wherein the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 1:1.5: 0.75:1:0.75.
The diffusion-resistant high-entropy alloy coating material according to claim 1 or 2, wherein the ratio of Al, Co, Cr, Ni and Mo in the diffusion-resistant high-entropy alloy coating is 0.9:0.9: 1:1:1.2.
The diffusion-resistant high-entropy alloy coating material according to claim 1 or 2, wherein the Al, Co, Cr, Ni and Mo of the diffusion-resistant high-entropy alloy coating are in an atomic percentage ratio of 0.8:1.1: 0.9:1.2:1.
The diffusion-resistant high-entropy alloy coating material according to any one of claims 1 to 8, wherein the diffusion-resistant high-entropy alloy coating material is a single-phase solid solution or an amorphous phase structure.
The diffusion-resistant high-entropy alloy coating material according to any one of claims 1-9, wherein the base material is a superalloy; more preferably, the base material is an iron-based superalloy, a nickel-based high-temperature alloy Alloys or cobalt-based superalloys.
A preparation method for preparing the diffusion-resistant high-entropy alloy coating material according to any one of claims 1-10, characterized in that, comprising: forming the diffusion-resistant high-entropy alloy coating on the surface of the substrate.
The preparation method according to claim 11, wherein the forming the diffusion-resistant high-entropy alloy coating on the surface of the substrate comprises preparing Al, Co, Cr, Ni and Mo into a single alloy target, Then, the single alloy target is formed on the surface of the substrate by magnetron sputtering or arc ion plating to form the diffusion-resistant high-entropy alloy coating.
The preparation method according to claim 12, wherein the single alloy target is prepared by smelting or powder metallurgy.
The preparation method according to any one of claims 11-13, wherein the thickness of the diffusion-resistant high-entropy alloy coating is 2 μm-8 μm, preferably 2 μm-7 μm, more preferably 2 μm-6 μm, and more It is preferably 2 μm to 5 μm, and more preferably 2 μm to 4 μm.
The preparation method according to any one of claims 11-14, characterized in that, when the diffusion resistance high-entropy alloy coating is formed by means of magnetron sputtering, the background vacuum degree is less than or equal to 5×10 -3 Pa, substrate temperature 100-300℃;

Preferably, the target power is 200-300W, the DC bias of the substrate is -100--500V, the duty cycle is 60-90%, the target-base distance is 10-15cm, the working argon gas pressure is 0.6-0.8Pa, and the ion source is 0.8 -1.2A.
The preparation method according to any one of claims 11-14, characterized in that, when forming the diffusion-resistant high-entropy alloy coating by means of arc ion plating, the background vacuum degree is less than or equal to 5×10 − 3 Pa, under the conditions of substrate temperature 200-400 ℃;

Preferably, the target current is 70-90A, the DC bias of the substrate is -100--500V, the duty cycle is 60-90%, the target-base distance is 20-30cm, the working argon gas pressure is 1-1.3Pa, and the permanent magnet strength is 1500 -2000Gs, solenoid voltage 20-30V.
The preparation method according to any one of claims 11-16, further comprising: pre-processing the substrate before forming the diffusion-resistant high-entropy alloy coating on the surface of the substrate, The pretreatment includes: grinding and polishing the surface of the substrate, then ultrasonic cleaning with acetone, alcohol and deionized water respectively, and drying.
A high temperature resistant coating material, characterized in that it comprises a material body and a high temperature resistant coating applied on the material body, wherein the material body is the resistance of any one of claims 1-10 A diffusion-resistant high-entropy alloy coating material or a diffusion-resistant high-entropy alloy coating material prepared by the preparation method according to any one of claims 11-17;

Preferably, the high temperature resistant coating is PtAl coating, NiAl coating, NiAlHf coating, NiCrAlY coating, CoCrAlY coating, NiAlPtNb coating, NiAlHfRu coating, CoCrAlYSi coating, NiCoCrAlYTa coating, NiCrAlYLaB coating, Any of NiCoCrAlYHf coating and NiCoCrAlYTaRe coating.
The method for preparing a high temperature resistant coating material according to claim 18, characterized by comprising preparing the high temperature resistant coating on the surface of the material body;

Preferably, the method for preparing the high temperature resistant coating is selected from magnetron sputtering, electron beam physical vapor deposition, arc ion plating, flame spraying, atmospheric plasma spraying, vacuum plasma spraying, cold spraying, plasma spraying-physical vapor deposition and At least one of pulse plating.
Application of the high temperature resistant coating material described in claim 18 or the high temperature resistant coating material prepared by the preparation method described in claim 19 in the preparation of aero-engine or gas turbine hot-end components.