CN114411094B - High-entropy alloy nitride nano composite coating with cavitation erosion resistance and preparation method thereof - Google Patents

High-entropy alloy nitride nano composite coating with cavitation erosion resistance and preparation method thereof Download PDF

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CN114411094B
CN114411094B CN202111680533.5A CN202111680533A CN114411094B CN 114411094 B CN114411094 B CN 114411094B CN 202111680533 A CN202111680533 A CN 202111680533A CN 114411094 B CN114411094 B CN 114411094B
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entropy alloy
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nitride
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徐江
彭爽
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Nanjing University of Aeronautics and Astronautics
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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
    • C23C14/3471—Introduction of auxiliary energy into the plasma
    • C23C14/3478—Introduction of auxiliary energy into the plasma using electrons, e.g. triode sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

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Abstract

The invention relates to a high-entropy alloy nitride nano composite coating with cavitation erosion resistance and a preparation method thereof. And forming a high-entropy alloy nitride coating with a nano composite structure on the surface of the Ti-6Al-4V alloy workpiece by adopting a double-cathode plasma sputtering deposition process. The adjustable technological parameters of the double cathode plasma sputtering deposition are target voltage, workpiece voltage, distance between workpiece and target (polar distance), working air pressure, argon-nitrogen flow ratio and deposition time. The high-entropy alloy nitride coating consists of a nitride phase and a high-entropy alloy solid solution phase, and has a layered nano composite structure. The coating improves the mechanical property and corrosion resistance of the surface of the workpiece. Compared with the workpiece material, the coating has longer cavitation and inoculation period and lower cavitation loss weight, and prolongs the service life of the workpiece in cavitation corrosion environment.

Description

High-entropy alloy nitride nano composite coating with cavitation erosion resistance and preparation method thereof
Technical Field
The invention relates to a high-entropy alloy coating and a preparation method thereof, in particular to a high-entropy alloy nitride nano composite coating with cavitation erosion resistance and a preparation method thereof.
Background
Cavitation is a common problem in over-flow components such as valves, pump impellers, water turbines, ship propellers and blades. In hydrodynamic environments, the liquid flowing over the surface of the component typically has strong pressure fluctuations due to high flow rates and turbulent flow. The local low pressure promotes nucleation and growth of cavitation bubbles in the liquid. As the liquid flows, these cavitation bubbles collapse when transferred to a high pressure region. Microjets and shock waves generated by cavitation collapse can cause localized impact loads on the surface of the material. With repeated formation and collapse of cavitation bubbles, the surface of the material is subjected to high-frequency impact, and fatigue damage is generated. In addition, impact force generated by cavitation collapse can also cause damage of a passivation film on the surface of the material, so that electrochemical corrosion reaction of the surface is accelerated. The synergistic effect between electrochemical corrosion and mechanical impact greatly increases cavitation damage of the material in the corrosive medium. Therefore, the improvement of cavitation erosion resistance of the material is a key for prolonging the service time of the overcurrent part. Cavitation erosion resistance of a material cannot be associated with a single performance index, and is related to various factors such as hardness, yield strength, strain hardening rate, fatigue strength, corrosion resistance and the like. Recent studies on high-entropy alloys have shown that high-entropy alloys have better strength, toughness and corrosion resistance than conventional alloys. The nitrogen element is doped in the high-entropy alloy, so that the mechanical property and the corrosion resistance of the alloy can be further improved, and the alloy is expected to become an excellent cavitation erosion resistant material.
Disclosure of Invention
The invention aims to: the invention aims to provide a high-entropy alloy nitride nano composite coating with longer cavitation and inoculation period, lower cavitation loss weight and prolonged service life of a workpiece.
Another object of the present invention is to provide a method for preparing the high entropy alloy nitride nanocomposite coating.
The technical scheme is as follows: the preparation method of the high-entropy alloy nitride nano composite coating utilizes a double-cathode plasma sputtering deposition technology to form a (TiZrHfMoW) N coating with a nano composite structure on the surface of a Ti-6Al-4V alloy workpiece.
Further, the target material is prepared by mixing high-purity metal powder of Ti, zr, hf, mo and W with the purity of more than or equal to 99.9 percent and the grain diameter of 300 meshes and then carrying out vacuum hot-pressing sintering, wherein the component proportion of the high-purity metal powder is 8.01wt.% Ti,15.27wt.% Zr,29.88wt.% Hf,16.06wt.% Mo and 30.78% W.
Further, the adjustable process parameters of the double cathode plasma sputtering deposition are as follows: target voltage is 850-950V, workpiece voltage is 250-350V, polar distance is 10mm, working air pressure is 25-35Pa, flow ratio of argon to nitrogen is 20:1, and deposition time is 3-3.5h.
The invention adopts a double cathode plasma sputtering deposition technology to prepare the (TiZrHfMoW) N high-entropy alloy nitride coating with cavitation erosion resistance on the surface of the Ti-6Al-4V alloy. The coating consists of a BCC solid solution phase enriched in Ti, zr and Hf elements and a nitride phase enriched in Mo and W. And the nitride phase of the lamellar structure in the coating is distributed with the solid solution phase of the high-entropy alloy so as to form a nano composite structure. In cavitation experiments based on ASTM-G32 standard, the coating shows lower weight loss and longer cavitation incubation period in 3.5wt% NaCl solution than Ti-6Al-4V alloy, and the cavitation resistance of the matrix alloy is greatly improved.
The (TiZrHfMoW) N high-entropy alloy nitride coating prepared by adopting the double-cathode plasma sputtering deposition technology has a nano layered composite structure. As shown in fig. 1, the Mo and W enriched nitride layer is interphase distributed with the Ti, zr and Hf enriched high entropy solid solution phase. The layered structure can deflect the vertical expansion of cracks, absorb more impact energy generated by cavitation bubbles, and simultaneously slow down the penetration of corrosive media.
The (TiZrHfMoW) N high-entropy alloy nitride coating can improve the surface hardness and the elastic modulus of the Ti-6Al-4V alloy. The existence of nitride and solid solution of N element in the (TiZrHfMoW) N high-entropy alloy nitride coating enable the coating to have higher hardness and modulus. As shown in FIG. 2, the hardness of the coating is 18.8+/-0.6 GPa, the elastic modulus is 199.6+/-7.5 GPa, which is far higher than that of a Ti-6Al-4V alloy with the hardness of 5.8+/-0.3 GPa and the elastic modulus of 130.5+/-4.1 GPa.
The (TiZrHfMoW) N high-entropy alloy nitride coating can improve the corrosion resistance of the Ti-6Al-4V alloy. As shown in fig. 3, the coating had a lower self-corrosion potential and self-corrosion current density than the Ti-6Al-4V alloy in a 3.5wt.% NaCl solution.
The (TiZrHfMoW) N high-entropy alloy nitride coating can improve cavitation corrosion resistance of the Ti-6Al-4V alloy. As shown in fig. 4, the cumulative loss weight of the coating was less than Ti-6Al-4V alloy in a 3.5wt.% NaCl solution and the cavitation incubation period was longer.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the nano layered composite structure can deflect the vertical expansion of cracks, absorb more impact energy generated by cavitation bubbles, and simultaneously slow down the penetration of corrosive media.
2. The coating provided by the invention can improve the surface hardness and the elastic modulus of the Ti-6Al-4V alloy.
3. The coating provided by the invention can improve the corrosion resistance of Ti-6Al-4V alloy.
4. Compared with Ti-6Al-4V alloy, the coating provided by the invention has lower weightlessness and longer cavitation-corrosion inoculation period, and can effectively prolong the service life of a workpiece in cavitation-corrosion environment.
Drawings
FIG. 1 is a STEM image of a (TiZrHfMoW) N high entropy alloy nitride coating and a mapping picture of elements Ti, zr, hf, mo, W and N;
FIG. 2 is a graph of load displacement of the high entropy alloy nitride nanocomposite coating and Ti-6Al-4V alloy in a nanoindentation test with a maximum load of 40 mN;
FIG. 3 is a plot of the potentiodynamic polarization of the high-entropy alloy nitride nanocomposite coating and Ti-6Al-4V alloy in 3.5wt.% NaCl solution;
FIG. 4 is a plot of cumulative weight loss of the high entropy alloy nitride nanocomposite coating and Ti-6Al-4V alloy as a function of cavitation time under cavitation test conditions of ASTM-G32 standard and in 3.5wt.% NaCl solution;
fig. 5 (tizrshfmow) is a cross-sectional SEM image of an N high entropy alloy nitride coating.
Detailed Description
Example 1:
the preparation process of the (TiZrHfMoW) N high-entropy alloy nitride coating utilizes a double-cathode plasma sputtering deposition method, and the coating formed on the surface of the Ti-6Al-4V alloy workpiece consists of a nitride phase and a high-entropy alloy solid solution phase and has a layered nano composite structure. Wherein the method comprises the steps of
a. Parameters of the double cathode plasma sputtering process:
Figure BDA0003445570360000031
b. sputtering target: mixing Ti-Zr-Hf-Mo-W target, wherein the components are proportioned (mass fraction): 8.01wt.% Ti,15.27wt.% Zr,29.88wt.% Hf,16.06wt.% Mo,30.78% w;
c. the type of workpiece material: ti-6Al-4V alloy.
FIG. 1 is a STEM image of a (TiZrHfMoW) N high entropy alloy nitride coating, and a mapping picture of the elements Ti, zr, hf, mo, W and N. STEM pictures show that the coating consists of two phases and has a nanolayered structure. Wherein the high-entropy alloy solid solution phase is rich in Ti, zr and Hf elements, and the nitride phase is rich in Mo and W elements. The coating exhibits a smaller indentation depth and a greater elastic recovery than the Ti-6Al-4V alloy in the nano indentation test with a maximum load of 40N. Indicating that the coating absorbs more impact energy. The hardness of the coating is 18.8+/-0.6 GPa, the elastic modulus is 199.6+/-7.5 GPa, which is far higher than the Ti-6Al-4V alloy with the hardness of 5.8+/-0.3 GPa and the elastic modulus of 130.5+/-4.1 GPa. In a 3.5wt.% NaCl solution, the coating has a lower self-corrosion potential and self-corrosion current density than Ti-6Al-4V alloys, exhibiting excellent corrosion resistance. The coating has a smaller total loss weight and a longer cavitation incubation period than the Ti-6Al-4V alloy under cavitation test conditions of the ASTM-G32 standard and in a 3.5wt.% NaCl solution. The high-entropy alloy nitride nano composite coating prepared by the double-cathode plasma sputtering deposition method can effectively slow down cavitation damage of a workpiece in a corrosive environment.
Example 2:
the preparation process of the high-entropy alloy nitride nano composite coating utilizes a double-cathode plasma sputtering deposition method to form a nano composite coating with a layered structure, which is formed by a nitride phase and a high-entropy alloy solid solution phase, on the surface of a Ti-6Al-4V alloy workpiece. Wherein a. Technological parameters of double cathode plasma sputtering deposition: target voltage 850V, workpiece voltage 250V, polar distance 10mm, working air pressure 35Pa, argon to nitrogen flow ratio 20:1, deposition temperature 700-800 ℃ and deposition time 3.5h. b. Mixing Ti-Zr-Hf-Mo-W target, wherein the components are proportioned (mass fraction): 8.01wt.% Ti,15.27wt.% Zr,29.88wt.% Hf,16.06wt.% Mo,30.78% w; c. the type of workpiece material: ti-6Al-4V alloy. The overall properties of the resulting coating were slightly lower than in example 1.
Example 3:
the preparation process of the high-entropy alloy nitride nano composite coating utilizes a double-cathode plasma sputtering deposition method to form a nano composite coating with a layered structure, which is formed by a nitride phase and a high-entropy alloy solid solution phase, on the surface of a Ti-6Al-4V alloy workpiece. Wherein a. Technological parameters of double cathode plasma sputtering deposition: the target voltage is 950V, the workpiece voltage is 350V, the polar distance is 10mm, the working air pressure is 25Pa, the flow ratio of argon to nitrogen is 20:1, the deposition temperature is 700-800 ℃, and the deposition time is 3h. b. Mixing Ti-Zr-Hf-Mo-W target, wherein the components are proportioned (mass fraction): 8.01wt.% Ti,15.27wt.% Zr,29.88wt.% Hf,16.06wt.% Mo,30.78% w; c. the type of workpiece material: ti-6Al-4V alloy. The overall properties of the resulting coating were slightly lower than in example 1.

Claims (2)

1. A preparation method of a high-entropy alloy nitride nano composite coating with cavitation erosion resistance is characterized by comprising the following steps: a double cathode plasma sputtering deposition process is adopted, the target voltage is controlled to be 850-950 and V, the workpiece voltage is controlled to be 250-350V, the polar distance is controlled to be 10mm, the working air pressure is controlled to be 25-35 and Pa, the flow ratio of argon to nitrogen is 20:1, the deposition time is 3-3.5h, the deposition temperature is 700-800 ℃, a high-entropy alloy nitride coating with a nano composite structure is formed on the surface of a Ti-6Al-4V alloy workpiece, the coating consists of a BCC solid solution phase enriched with Ti, zr and Hf elements and a nitride phase enriched with Mo and W, and the nitride phase of a layered structure in the coating and the high-entropy alloy solid solution phase are distributed alternately to form a nano composite structure; the target material is prepared by mixing high-purity metal powder of Ti, zr, hf, mo and W with the purity of more than or equal to 99.9 percent and the grain diameter of 300 meshes and then carrying out vacuum hot-pressing sintering, wherein the component proportion of the high-purity metal powder is 8.01wt percent of Ti,15.27wt percent of Zr,29.88wt percent of Hf,16.06wt percent of Mo and 30.78 percent of W.
2. A high entropy alloy nitride nanocomposite coating having cavitation erosion resistance, prepared by the method of claim 1.
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