Dense-packed lattice core-shell structure multi-principal element alloy material, preparation method and application thereof

Abstract

This invention provides a close-packed lattice core-shell structured multi-principal element alloy material, its preparation method, and its applications. The elemental composition of the multi-principal element alloy material satisfies Al... a Co b Cr c Fe d Ni e Nb f Ti g The alloy exhibits the following properties: 0.01≤a≤0.3, 0.5≤b≤1.2, 0.5≤c≤1.2, 0.5≤d≤1.2, 0.5≤e≤1, 0.2≤f≤0.5, 0.1≤g≤0.5. Furthermore, it possesses a dual-phase core-shell structure with a coordinated distribution of highly corrosion-resistant elements, comprising an FCC-structured solid solution core and an HCP-structured shell. The core and shell are heterogeneous two phases, both possessing a close-packed lattice. The core is enriched with the primary highly corrosion-resistant element Cr, while the shell is enriched with the secondary highly corrosion-resistant elements Nb and Ti. This multi-principal element alloy material demonstrates excellent synergistic strength and toughness, strong resistance to pitting corrosion, and excellent resistance to erosion-coupled damage, making it suitable for protecting key components of marine equipment from surface wear, corrosion, or erosion-coupled damage.

Description

Technical Field

[0001] This invention relates to the field of surface protection technology, specifically to a dense-packed lattice core-shell structure multi-principal-element alloy material, its preparation method, and its application. Background Technology

[0002] Key underwater transmission components such as ship stern shafts, underwater vehicle main shafts, and underwater robot pins are subjected to alternating stresses, heavy-load friction, and corrosion interactions in the seawater environment for extended periods, and generally face the challenge of coupled mechanical-electrochemical corrosion damage.

[0003] The harsh operating conditions of seawater environment, characterized by the interaction of mechanical and electrochemical corrosion, place inherent demands on protective coatings to achieve strong adhesion, corrosion resistance, and wear resistance—all integrated into a single, multifunctional component. Currently, preparing metallurgically bonded alloy coatings using high-energy beam coating technologies (such as laser cladding and welding) is a common approach to protecting components from surface damage and is considered a crucial technology for improving the wear and corrosion resistance of key underwater transmission components in major marine equipment. However, existing traditional alloy materials and multi-principal alloys (i.e., high-entropy alloys) generally face a contradiction between strength and toughness, as well as a balance between mechanical / wear- and corrosion-resistant properties. Compared to traditional alloy coatings such as cobalt-based and iron-based alloys, multi-principal alloys offer advantages such as simple phase structures and a large space for composition and structure control. However, a series of studies have shown that the differences in electrochemical properties between heterogeneous phases in multi-principal alloys easily induce "corrosion micro-cells" or localized non-uniform corrosion phenomena, leading to insufficient corrosion resistance in surface coating applications and difficulty in balancing wear and corrosion resistance. This is a significant reason hindering their application in the field of wear and corrosion protection in complex marine environments. Summary of the Invention

[0004] To solve all or part of the above-mentioned technical problems, the present invention provides the following technical solutions:

[0005] The first aspect of the present invention provides a close-packed lattice core-shell structured multi-principal element alloy material whose elemental composition satisfies Al a Co b Cr c Fe d Ni e Nb f Ti g a, b, c, d, e, f, g represent the molar ratios of the elements, where 0.01≤a≤0.3, 0.5≤b≤1.2, 0.5≤c≤1.2, 0.5≤d≤1.2, 0.5≤e≤1, 0.2≤f≤0.5, and 0.1≤g≤0.5.

[0006] The multi-principal-element alloy material has a dual-phase core-shell structure, which includes an FCC-structured solid solution cell core and an HCP-structured shell. The core and shell are heterogeneous two phases, and both phases have a close-packed lattice.

[0007] The core and cladding contain a coordinated distribution of highly corrosion-resistant elements, which includes: the core being enriched with a first highly corrosion-resistant element, which includes Cr; and the cladding being enriched with a second highly corrosion-resistant element, which includes Nb and Ti.

[0008] On the one hand, the aforementioned dense-packed lattice core-shell multi-principal alloy material exhibits a coordinated distribution of highly corrosion-resistant elements between the heterogeneous core and shell phases, resulting in a unique internal oxidation-dominated passivation mechanism under seawater corrosion. On the other hand, the core and shell structures of this multi-principal alloy material also possess high mechanical compatibility, exhibiting heterogeneous phase synergistic plastic flow and synergistic nano-refinement under friction or stress. Benefiting from the aforementioned coordinated distribution of highly corrosion-resistant elements and high mechanical compatibility within the dual-phase core-shell structure, this multi-principal alloy material demonstrates excellent synergistic strength and toughness, strong resistance to pitting corrosion, and excellent resistance to erosion coupling damage in seawater environments.

[0009] The aforementioned highly corrosion-resistant elements exhibit a coordinated distribution across the core-shell heterogeneous phases of multi-principal element alloys. Specifically, the FCC-structured solid solution core and the HCP-structured shell are enriched with the primary highly corrosion-resistant element Cr, and the secondary highly corrosion-resistant elements Nb and Ti, respectively. This enhances the density and stability of the initial oxide film on the coating surface, thereby enabling it to effectively resist Cl in seawater environments. - The corrosion process hinders the anodic oxidation and dissolution of Fe, Cr, and other atoms within the coating, activating a unique internal oxidation-dominated passivation mechanism. Therefore, unlike the passivation film formation mechanism of metal ion reduction deposition commonly found in existing metallic materials in seawater environments, the anti-wear coating based on the aforementioned multi-principal-element alloy material provided by this invention possesses a unique internal oxidation-dominated passivation mechanism. The passivation film formed by internal oxidation exhibits significantly improved density and stability compared to traditional metal ion reduction deposition films, effectively inhibiting the formation of corrosion microcells and enabling the coating to possess excellent resistance to localized corrosion or pitting corrosion in static seawater corrosion environments.

[0010] The high mechanical compatibility of the multi-principal element alloy material stems from at least two aspects: Firstly, the solid solution nucleus of the FCC close-packed structure has a low stacking fault energy, exhibiting high dislocation and stacking fault activation and storage capacity under low frictional strain, resulting in excellent plasticity and hardening properties. As the frictional strain level increases, the interaction between dislocations and twins not only provides additional hardening but also enables efficient dynamic recrystallization, allowing grain size to be refined to the nanometer scale, effectively resisting wear damage. Secondly, the heterogeneous second-phase cladding of the HCP close-packed structure and the solid solution nucleus of the FCC close-packed structure exhibit good mechanical matching and compatibility. During the friction deformation process, the heterogeneous interface between the heterogeneous second-phase shell and the solid solution cell nucleus can provide nucleation sites for crystal plastic defects such as dislocations and twins during the friction and wear process, while the solid solution cell nucleus is refined to the nanoscale. Furthermore, as the friction strain further increases, the refined heterogeneous second-phase shell can continue to cooperate with the solid solution cell in plastic flow under the action of shear stress at the friction interface, and dynamically recrystallize with the nanoscale surface layer of the wear area, resulting in a tight bond between the grains, which is beneficial to improving the load-bearing capacity and wear resistance of the coating.

[0011] In some embodiments, the percentage of Cr atoms enriched in the core is 16% to 25%, while the percentage of Cr atoms in the shell is only 10% to 14%.

[0012] In some embodiments, the Cr content in the shell is lower than the Cr content in the core. For example, the atomic percentage of Cr in the shell is less than 14%, and in some embodiments it is 10% to 14%.

[0013] In some embodiments, the atomic percentage content of Nb enriched in the shell is 5% to 16%, and the atomic percentage content of Ti is 5% to 16%.

[0014] In some embodiments, the atomic percentages of Nb and Ti in the core are lower than those in the shell. For example, the atomic percentages of Nb and Ti in the core are only 0.3% to 4% and 0.3% to 4%, respectively.

[0015] In some embodiments, Co, Ni, and Al in the multi-principal alloy material are uniformly distributed between the core and the shell phases; Fe and Cr have the same distribution characteristics, that is, the atomic percentage of Fe in the core is greater than that in the shell, forming an FCC structure FeCr solid solution core, wherein the atomic percentage of Fe in the core is 26%~35% and the atomic percentage of Fe in the shell is 19%~25%.

[0016] In some embodiments, the HCP structure encapsulates the FCC structure solid solution cell core in a completely continuous or near-continuous state.

[0017] In some embodiments, the diameter of the core of the FCC structure solid solution cell is 5μm to 50μm.

[0018] In some embodiments, the volume fraction of the cladding in the dense-packed lattice core-shell structured multi-principal-element alloy material is 8% to 20%, for example, 10% to 19.5%.

[0019] In some embodiments, the self-corrosion current density of the dense-packed lattice core-shell structured multi-principal-element alloy material in a seawater environment reaches 10. -8 A / cm -2 Magnitude.

[0020] In some embodiments, the pitting potential of the close-packed lattice core-shell structure multi-principal-element alloy material relative to the saturated calomel electrode is above 1000 mV.

[0021] In some embodiments, the wear rate of the close-packed lattice core-shell structure multi-principal element alloy material is 5 × 10⁻⁶. -6 mm 3 / N·m and below.

[0022] A second aspect of the present invention provides an anti-abrasion coating comprising a close-packed lattice core-shell structure multi-principal element alloy material as described in any of the technical solutions.

[0023] The aforementioned anti-abrasion coating is suitable for protecting critical components of marine equipment from surface wear, corrosion, or abrasion-corrosion coupled damage.

[0024] In some embodiments, the surface of the anti-abrasion coating has a passivation film formed by the anti-abrasion coating in a seawater environment based on an internal oxidation-dominated passivation mechanism.

[0025] A third aspect of the present invention provides an anti-abrasion structure comprising a substrate and a coating structure bonded to the substrate, the coating structure comprising the anti-abrasion coating described in any of the technical solutions.

[0026] A fourth aspect of the present invention provides a method for preparing an anti-wear structure, comprising:

[0027] Provide a multi-principal component powder material, wherein the elements contained in the multi-principal component powder material satisfy Al a Co b Cr c Fe d Ni e Nb f Ti ga, b, c, d, e, f, g represent the molar ratios of the elements, where 0.01≤a≤0.3, 0.5≤b≤1.2, 0.5≤c≤1.2, 0.5≤d≤1.2, 0.5≤e≤1, 0.2≤f≤0.5, and 0.1≤g≤0.5.

[0028] The multi-principal element powder material is clad onto a substrate using laser cladding technology to form an anti-abrasion coating with a densely packed lattice core-shell structure, thereby obtaining the anti-abrasion structure.

[0029] The multi-principal alloy material with the above-mentioned components has low Al, Nb, and Ti content and high content of self-dissolving alloying elements Ni, Co, and Fe. It has good forming ability in the non-equilibrium rapid solidification process of laser cladding manufacturing technology, and can form an anti-wear coating based on the core-shell structure of the multi-principal alloy material with a close-packed lattice. Moreover, the anti-wear coating has a strong metallurgical bond with the substrate and is highly dense.

[0030] In some embodiments, the process conditions of the laser cladding technology include: laser power of 600 W to 900 W, spot diameter of 1 mm to 1.5 mm, scanning speed of 9 mm / s to 11 mm / s, overlap rate of 40% to 60%, powder feeding speed of 11 r / min to 13 r / min, and protective gas flow rate of 13 L / min to 16 L / min. The above-mentioned laser cladding technology can form a highly dense, wear-resistant coating with strong metallurgical bonding on the substrate.

[0031] In some embodiments, the substrate is preheated to 250°C to 450°C before cladding is performed. Setting the preheating temperature to 250°C to 450°C reduces the coating cooling rate and the temperature gradient between the coating and the substrate, thereby reducing cladding thermal stress. Simultaneously, it prolongs the mass transfer process of large-diameter atoms such as Nb and Ti during solidification, which is beneficial for the highly uniform formation of core-shell structures and the uniform distribution of highly corrosion-resistant elements between heterogeneous phases. Heating of the workpiece substrate can be achieved, for example, through a constant-temperature heating stage or an electromagnetic accompanying heating system.

[0032] In some embodiments, the multi-principal component powder material is prepared by mixing elemental powders and / or by gas-atomized alloy powders.

[0033] For example, in the preparation process of elemental powder mixing, the elemental powders containing the coating elements are placed in a planetary ball mill device, the material-to-ball ratio is set to 1:8 to 1:15, and the ball milling is carried out for 1 to 3 hours; then the obtained powder is dried in a vacuum drying oven at a temperature of, for example, 150 to 300°C for 0.5 to 2 hours, so as to obtain multi-principal alloy powder with good sphericity and uniform mixing, to ensure powder flowability and facilitate the uniform distribution of elements in the molten pool during the cladding process.

[0034] In some embodiments, the multi-principal component powder material is obtained by mixing CoCrFeNi alloy powder with Al, Nb, and Ti elemental powders according to the required elemental molar ratio.

[0035] In some embodiments, the powder size of the multi-principal component powder material is 45μm to 150μm. Powders within this size range have high compatibility with cladding processes and low manufacturing costs.

[0036] In some embodiments, the substrate material includes one or a combination of stainless steel and high-strength martensitic steel. The aforementioned substrate material exhibits good elemental compatibility and similar thermophysical parameters to the anti-wear and corrosion coating provided by this invention, enabling high-quality manufacturing of the surface coating and enhancing its wear and corrosion resistance in seawater environments.

[0037] The fifth aspect of the present invention provides an anti-abrasion structure, which is prepared by the preparation method described in any of the above technical solutions.

[0038] A sixth aspect of the present invention provides a transmission component for marine equipment, comprising the anti-abrasion structure described in any of the technical solutions.

[0039] A seventh aspect of the present invention provides a marine device comprising the anti-abrasion structure described in any of the technical solutions.

[0040] The aforementioned marine equipment can be marine air and sea equipment, marine equipment, or marine underwater equipment. Marine air and sea equipment includes, but is not limited to, island-based aircraft and sea-based aircraft; marine equipment includes, but is not limited to, ships and marine engineering equipment; and underwater equipment includes, but is not limited to, underwater vehicles, deep-sea mining hoisting systems, and deep-sea mining vehicles.

[0041] Compared with the prior art, the present invention has at least some or all of the following beneficial effects:

[0042] (1) The dense-packed lattice core-shell structure multi-principal element alloy material provided by the present invention has the characteristic of high corrosion-resistant elements being coordinated and distributed between the core and shell heterogeneous phases, and exhibits a special internal oxidation-dominated passivation mechanism under seawater corrosion.

[0043] (2) The core-shell structure of the multi-principal alloy material provided by the present invention also has high mechanical compatibility, and it exhibits heterogeneous phase synergistic plastic flow and synergistic nano-refinement under friction or stress.

[0044] (3) The multi-principal alloy material provided by the present invention benefits from the coordinated distribution characteristics of high corrosion-resistant elements and high mechanical compatibility in the dual-phase core-shell structure, exhibiting excellent strong and tough synergistic effect, strong resistance to pitting corrosion, and excellent resistance to wear and erosion coupling damage in seawater environment.

[0045] (4) The present invention utilizes cladding manufacturing technology to enable multi-principal powder materials to form a dual-phase core-shell structure with a dense lattice under non-equilibrium rapid solidification conditions.

[0046] (5) The anti-abrasion coating provided by the present invention is suitable for application on the surface of marine equipment (such as transmission components of marine equipment) to protect against wear, corrosion or abrasion coupling damage. Attached Figure Description

[0047] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0048] Figure 1 This is a microstructure diagram of the anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy prepared in Example 1;

[0049] Figure 2 The XRD pattern of the anti-abrasion coating of Example 1 is shown below.

[0050] Figure 3 This is an EDS surface scan of the anti-abrasion coating of Example 1;

[0051] Figure 4 These are the results of the potentiodynamic polarization test of the anti-abrasion coatings prepared in Examples 1-3 in an artificial seawater environment;

[0052] Figure 5 This is a TEM image of the passivation film on the surface of the anti-abrasion coating obtained in Example 1;

[0053] Figure 6 The diagram shows the volumetric wear rate of the anti-abrasion coatings prepared in Examples 1-3 in an artificial seawater environment.

[0054] Figure 7 This is a TEM cross-sectional image of the second surface area of ​​the anti-abrasion coating of Example 1 after abrasion testing in a seawater environment;

[0055] Figure 8 This is a TEM image of the surface area of ​​the anti-abrasion coating of Example 1 after abrasion testing in a seawater environment.

[0056] Figure 9 This is an SEM image of the coating obtained in Comparative Example 1;

[0057] Figure 10 This is an SEM image of the coating obtained in Comparative Example 2. Detailed Implementation

[0058] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the claims of the present invention.

[0059] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0060] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventionally understood meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed through conventional methods.

[0061] In addition, unless otherwise specified, all raw materials used in the following embodiments can be purchased from the market or other sources, and all production and testing equipment used are known in the art, as are the testing methods used.

[0062] The relevant testing methods and instruments involved in the following specific embodiments of the present invention are as follows:

[0063] (1) Scanning electron microscopy images and elemental distribution analysis: The microstructure and elemental distribution characteristics of the coating were observed using a FEI Quanta FEG 250 scanning electron microscope (SEM).

[0064] (2) XRD test: The phase structure of the coating was analyzed by XRD diffractometer. Radial scanning was performed from 20° to 90° at a scattering angle of 2θ, and the scanning speed was 4° / min.

[0065] (3) Corrosion resistance test: The corrosion resistance test was conducted using a Gamry electrochemical workstation with a three-electrode system. The polished samples from Examples 1-3 were used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the glass slide was used as the counter electrode.

[0066] (4) Seawater environment abrasion performance test: In-situ friction-corrosion tester was used under the following conditions: load 10 N, friction frequency 3 Hz, friction time 0.5 h, and the corrosion solution was simulated artificial seawater (3.5 wt.% NaCl solution). The wear volume of the wear area was measured using a confocal microscope, and the volume wear rate of the sample was calculated by wear volume / (load × total stroke).

[0067] (5) Transmission electron microscopy images: The passivation film of the anti-wear coating of the core-shell multi-principal alloy and the microstructure characteristics of the surface and interface after wear in simulated seawater environment were observed using a ThemoFisher Talos F200x transmission electron microscope.

[0068] The technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0069] Example 1

[0070] This embodiment provides an anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy material and its preparation method, specifically including the following steps:

[0071] S1: According to the elemental composition formula Al 0.3 CoCrFeNiNb 0.3 Ti 0.3 CoCrFeNi alloy powder and Al, Nb and Ti elemental powders were weighed according to the molar ratio of the elements in the above formula. The powder size ranged from 45 to 150 μm. The weighed powder was placed in a planetary ball mill with a material-to-ball ratio of 1:15 and a milling time of 1 h. Then it was placed in a vacuum drying oven and dried at 200 °C for 1.5 h to obtain multi-principal element powder material.

[0072] S2: Clean the surface of GS80 high-strength martensitic steel substrate with alcohol and ethanol respectively, and then place the substrate on a constant temperature heating platform for preheating treatment at a temperature of 350℃.

[0073] S3: Coating is manufactured using a circular beam laser cladding process. A coaxial powder feeding method is used to deliver the aforementioned multi-principal element powder material onto the preheated substrate surface. The laser power is set to 700 W, the spot diameter to 1 mm, the scanning speed to 9 mm / s, the overlap rate to 50%, the powder feeding speed to 12 r / min, and the protective gas flow rate to 15 L / min. During this laser cladding process, the multi-principal element powder material undergoes non-equilibrium rapid solidification, reaching a density of 10... 6 ~10 8 A dense lattice core-shell structure is generated at a heating and cooling rate of K / s, forming an anti-abrasion coating with a thickness of about 1.5 mm on the substrate.

[0074] Example 2

[0075] The only difference between Example 2 and Example 1 is that Example 2 follows the elemental composition formula Al. 0.3 CoCrFeNiNb 0.4 Ti 0.2 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0076] Example 3

[0077] The only difference between Example 3 and Example 1 is that Example 3 is based on the elemental composition relationship Al. 0.3 CoCrFeNiNb 0.2 Ti 0.4 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0078] Example 4

[0079] The only difference between Example 4 and Example 1 is that Example 4 follows the elemental composition formula Al. 0.2 CoCrFeNiNb 0.3 Ti 0.3 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0080] Example 5

[0081] The only difference between Example 5 and Example 1 is that Example 5 is based on the elemental composition relationship Al. 0.2 CoCrFeNiNb 0.4 Ti 0.2 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0082] Example 6

[0083] The only difference between Example 6 and Example 1 is that Example 6 is based on the elemental composition relationship Al. 0.3 CoCrFe 0.9 NiNb 0.3 Ti 0.3 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0084] Example 7

[0085] The only difference between Example 7 and Example 1 is that Example 7 follows the elemental composition formula Al. 0.3 CoCrFe 0.9 NiNb 0.4 Ti 0.2 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0086] Example 8

[0087] The only difference between Example 8 and Example 1 is that Example 8 is based on the elemental composition formula Al. 0.3 CoCr 0.8 FeNiNb 0.3 Ti 0.3 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0088] Example 9

[0089] The only difference between Example 9 and Example 1 is that Example 9 is based on the elemental composition formula Al. 0.3 CoCr 0.8 FeNiNb 0.4 Ti 0.2 CoCrFeNi alloy powder was mixed with elemental powders of Al, Nb, and Ti to prepare multi-principal-element powder materials. The rest of the process was the same as in Example 1, and will not be repeated here.

[0090] Example 10

[0091] This embodiment provides an anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy material and its preparation method, specifically including the following steps:

[0092] S1: According to the elemental composition formula Al 0.3 CoCrFeNiNb 0.3 Ti 0.3 CoCrFeNi alloy powder and Al, Nb and Ti elemental powders were weighed according to the molar ratio of the elements in the above formula. The powder size ranged from 45 to 150 μm. The weighed powder was placed in a planetary ball mill with a material-to-ball ratio of 1:15 and a milling time of 1 h. Then it was placed in a vacuum drying oven and dried at 200 °C for 1.5 h to obtain multi-principal element powder material.

[0093] S2: Clean the surface of GS80 high-strength martensitic steel substrate with alcohol and ethanol respectively, and then place the substrate on a constant temperature heating platform for preheating treatment at a temperature of 250℃.

[0094] S3: The coating is manufactured using a circular beam laser cladding process. The above-mentioned multi-principal element powder material is spread on a preheated substrate. The laser power is set to 600 W, the spot diameter is 1 mm, the scanning speed is 9 mm / s, the overlap rate is 40%, the powder feeding speed is 11 r / min, and the protective gas flow rate is 13 L / min, forming an anti-abrasion coating on the substrate.

[0095] Example 11

[0096] This embodiment provides an anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy material and its preparation method, specifically including the following steps:

[0097] S1: According to the elemental composition formula Al 0.3 CoCrFeNiNb 0.3 Ti 0.3 CoCrFeNi alloy powder and Al, Nb and Ti elemental powders were weighed according to the molar ratio of the elements in the above formula. The powder size ranged from 45 to 150 μm. The weighed powder was placed in a planetary ball mill with a material-to-ball ratio of 1:15 and a milling time of 1 h. Then it was placed in a vacuum drying oven and dried at 200 °C for 1.5 h to obtain multi-principal element powder material.

[0098] S2: Clean the surface of GS80 high-strength martensitic steel substrate with alcohol and ethanol respectively, and then place the substrate on a constant temperature heating platform for preheating treatment at a temperature of 450℃.

[0099] S3: The coating is manufactured using a circular beam laser cladding process. The above-mentioned multi-principal element powder material is spread on a preheated substrate. The laser power is set to 900 W, the spot diameter is 1.5 mm, the scanning speed is 11 mm / s, the overlap rate is 60%, the powder feeding speed is 13 r / min, and the protective gas flow rate is 16 L / min, forming an anti-abrasion coating on the substrate.

[0100] Comparative Example 1

[0101] The only difference between Comparative Example 1 and Example 1 is that Comparative Example 1 increases the atomic molar ratio of Fe to 1.5, and its elemental composition relationship is: Al 0.3 CoCrFe 1.5 NiNb 0.3 Ti 0.3 The rest is the same as in Example 1, and will not be described again here.

[0102] Comparative Example 2

[0103] The only difference between Comparative Example 2 and Example 1 is that the atomic molar ratio of Nb in Comparative Example 2 is increased to 0.6, and its elemental composition relationship is: Al 0.3 CoCrFeNiNb 0.6 Ti 0.3 The rest is the same as in Example 1, and will not be described again here.

[0104] The element composition relationships satisfied by Examples 1-9 and Comparative Examples 1-2 are summarized in Table 1.

[0105] Table 1

[0106]

[0107] Note: In Table 1, the elements in the composition formulas are not labeled, which means that the molar ratio of the corresponding elements is "1".

[0108] Comparative Example 3

[0109] Comparative Example 3 uses the high-performance corrosion-resistant multi-principal-element alloy reported in US11466344B2 as a control, selecting the CoCrFeNi2Mo alloy described therein. 0.25 (A36) and the molybdenum-free alloy CoCrFeNi2 (A35) were used as control samples.

[0110] Comparative Example 4

[0111] Comparative Example 4 uses the dual-phase multi-principal element alloy reported in JP6566169B2 as a control, and selects six dual-phase multi-principal element alloys described therein as control samples, namely: Co 26.8 Cr 17.9 Fe 17.9 Ni 26.8 Ti 8.9 Mo 1.8 (M1F), Co 26.3 Cr 17.5 Fe 17.5 Ni 26.3 Ti 8.8 Mo 3.5 (M2F), Co 25.4 Cr 17.0 Fe 17.0 Ni 25.4 Ti 8.5 Mo 6.8 (M3F), Co 25.0 Cr 16.7 Fe 16.7 Ni 25.0 Ti 8.3 Mo 8.3 (M4F), Co 28.9 Cr 19.2 Fe19.2 Ni 23.0 Ti 7.7 Mo 1.9 (M5S), Co 31.3 Cr 20.8 Fe 20.8 Ni 18.8 Ti 6.3 Mo 2.1 (M6S).

[0112] All six control samples mentioned above have a body-centered cubic (SC) + face-centered cubic (FCC) biphase structure.

[0113] Comparative Example 5

[0114] Comparative Example 5 uses the seawater-resistant high-entropy alloy coating reported in CN120158743A as a control, and selects the following four samples described therein as control samples: 600℃ annealed FeCrCoMnSi 0.6 Coating - Pre-fabrication layer width 7mm (Si) 0.6 -7) Annealed FeCrCoMnSi at 600℃ 0.6 Coating - Pre-coated layer width 10 mm (Si) 0.6 -10), 600℃ annealed FeCrCoMnSi 0.6 Coating - Pre-fabrication layer width 15 mm (Si) 0.6 -15), 600℃ annealed FeCrCoMnSi 0.6 Coating - Pre-fabrication layer width 20 mm (Si) 0.6 -20).

[0115] Figure 1 This is a microstructure diagram of the anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy prepared in Example 1. From... Figure 1 It can be seen that the anti-wear coating consists of a solid solution cell core (the area marked by the dashed line) and a heterogeneous second-phase shell. The solid solution cell core has a size of 3~8μm, and the shell has a volume fraction of approximately 19.6%. Figure 2 The image shows the XRD pattern of the anti-abrasion coating of Example 1. Figure 3 This is an EDS surface scan of the anti-abrasion coating of Example 1. Combined with... Figure 2 , Figure 3 It can be seen that the solid solution nucleus in this anti-corrosion coating is an FCC-structured solid solution phase, rich in Cr, a highly corrosion-resistant element; according to Figure 3It is evident that the three highly corrosion-resistant elements, Cr, Nb, and Ti, are harmoniously distributed in the core and cladding. Specifically, the atomic percentage of Cr in the core region is approximately 21.4%, while the atomic percentage of Cr in the cladding region is only 13.3%. Furthermore, the heterogeneous second-phase cladding is an HCP-structured Laves phase, rich in highly corrosion-resistant elements such as Nb and Ti, with atomic percentages of Nb and Ti in the cladding of approximately 8.7% and 8.3%, respectively; while the atomic percentages of Nb and Ti in the core region are only approximately 2.2% and 2.1%, respectively. In addition, Co, Ni, and Al atoms are nearly uniformly distributed between the two phases. This demonstrates that the multi-principal-element alloy material contained in the anti-wear coating of this invention possesses a close-packed lattice core-shell structure, and that highly corrosion-resistant elements are harmoniously distributed between the heterogeneous phases.

[0116] Figure 4 The results of potentiodynamic polarization tests of the anti-abrasion coatings prepared in Examples 1-3 in an artificial seawater environment are shown. Figure 4 It can be seen that the self-corrosion current density of the anti-corrosion coatings in Examples 1-3 is all above 10 in the simulated artificial seawater (3.5 wt.% NaCl solution) environment. -8 A / cm -2 The pitting potentials are all greater than 1 V, with the pitting potential in Example 1 reaching 1.2 V.

[0117] Figure 5 This is a TEM image of the passivation film on the surface of the anti-abrasion coating obtained in Example 1. From... Figure 5 It can be seen that the oxide layer on the surface of the anti-wear coating is dense and smooth, exhibiting significant internal oxidation passivation structure characteristics, thus effectively inhibiting the diffusion and dissolution of Fe, Cr, and other ions in the seawater environment, as well as Cl. - Erosion. This demonstrates that the dominant passivation mechanism of the anti-abrasion coating of the present invention is an internal oxidation film formation mechanism, which differs from the passivation film formation mechanism of metal ion reduction deposition in existing metallic materials.

[0118] Figure 6 This is a graph showing the volumetric wear rate of the anti-abrasion coatings prepared in Examples 1-3 in an artificial seawater environment. Figure 6 As shown, the wear rates of the anti-wear coatings in seawater environments for Examples 1-3 are all within 5 × 10⁻⁶. -6 mm 3 / N·m and below.

[0119] Figure 7 This is a TEM cross-sectional image of the secondary surface area of ​​the anti-abrasion coating of Example 1 after seawater abrasion testing. Figure 7As can be seen, after seawater abrasion testing, the subsurface of the anti-abrasion coating underwent plastic deformation. The FCC structure solid solution cell nucleus dynamically recrystallized to the nanoscale size, and the originally continuously distributed micron-sized heterogeneous second phase shell (HCP structure Laves phase) was also refined to the nanoscale size and exhibited an island-like distribution pattern as the solid solution cell nucleus was refined to the nanoscale size.

[0120] Figure 8 This is a TEM image of the surface area of ​​the anti-abrasion coating of Example 1 after an abrasion test in a seawater environment. Figure 8 As can be seen, with the continued increase of frictional strain, the refined heterogeneous second-phase shell can still continue to flow plastically along the solid solution cell nucleus, exhibiting obvious shear elongation deformation along the sliding direction. This proves that the dual-phase core-shell structure of the multi-principal element alloy material provided by this invention has high mechanical compatibility and can significantly improve the load-bearing and anti-wear properties of the coating.

[0121] Figure 9 This is a SEM image of the coating prepared in Comparative Example 1. In Comparative Example 1, the atomic molar ratio of Fe was increased to 1.5, and the resulting coating exhibited a eutectic structure, making it impossible to prepare a multi-principal element alloy anti-wear coating with a close-packed lattice core-shell structure.

[0122] Figure 10 This is a SEM image of the coating obtained in Comparative Example 2. In Comparative Example 2, the atomic molar ratio of Nb was increased to 0.6, and it was found that the coating obtained under this condition showed obvious cracking and the forming quality was significantly reduced.

[0123] Table 2 summarizes the microstructure and electrochemical corrosion data of the coatings in the above embodiments and comparative examples.

[0124] Table 2. Microstructure and electrochemical corrosion data of samples obtained in Examples 1-9 and Comparative Examples 1-5

[0125] ;

[0126]

[0127] As shown in Table 2, the anti-corrosion coatings prepared in Examples 1-9 all consist of an FCC-structured solid solution core and an HCP-structured Laves heterogeneous second phase shell. The self-corrosion current density of these anti-corrosion coatings in simulated seawater (3.5 wt.% NaCl solution) environments is all above 10. -8 A / cm -2 The magnitudes and pitting potentials are all greater than 1 V.

[0128] The excessive Fe content in the coating of Comparative Example 1 led to the formation of a eutectic structure, resulting in significant microgalvanic corrosion and a decrease in the self-corrosion current density of the coating to 10. -7 A / cm -2 The pitting potential drops to approximately 0.72 V.

[0129] The coating of Comparative Example 2 had an excessively high Nb content, which caused the coating to crack and made it impossible to accurately measure the electrochemical data.

[0130] Although the FCC single-phase multi-principal alloy in Comparative Example 3 can avoid the corrosion microcell effect, its self-corrosion current density is only around 10. -7 A / cm -2 The corrosion resistance is on the order of magnitude higher than that of the anti-wear coating based on a close-packed lattice core-shell structure multi-principal element alloy material of the present invention. Furthermore, its maximum pitting potential is 0.91V, which is far lower than the pitting resistance level of the anti-wear coating of the embodiments of the present invention.

[0131] The maximum pitting potential of the dual-phase structure (SC+FCC) multi-principal alloy in Comparative Example 4 is only 0.9 V, which is significantly lower than that of the anti-wear coatings in Examples 1-9.

[0132] The multi-principal alloy coating involved in Comparative Example 5 has a multiphase structure of "FCC+BCC+silicide, etc." Even after stress-relief annealing, the coating still exhibits a high self-corrosion current density in seawater environments, reaching 10... -6 A / cm -2 Magnitude.

[0133] Table 3 summarizes the volumetric wear rate data of the coatings in the above embodiments and comparative examples in a simulated seawater environment.

[0134] Table 3. Volumetric wear rate data of the coatings prepared in simulated seawater environment for Examples 1-9 and Comparative Examples 1, 2, and 5.

[0135]

[0136] As shown in Table 3, the volumetric wear rate of the anti-abrasion coatings in Examples 1-9 under simulated seawater conditions is all within 5 × 10⁻⁶. -6 mm 3 The N·m value is below 10 N·m, indicating excellent anti-wear performance. In contrast, the multiphase multi-principal element alloy coating in Comparative Example 5 only achieved a wear rate of 10% in a seawater environment. -5 mm 3 The order of magnitude is on the order of N·m. This demonstrates that the close-packed lattice core-shell structure multi-principal element alloy material provided by this invention exhibits superior corrosion resistance in seawater environments.

[0137] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0138] In summary, the close-packed lattice core-shell structure multi-principal element alloy material provided by this invention has the significant characteristics of high corrosion resistance and coordinated distribution of heterogeneous phases, as well as high mechanical compatibility. Under seawater corrosion, it exhibits a special internal oxidation-dominated passivation mechanism. The close-packed lattice dual-phase core-shell structure can synergistically achieve plastic flow and synergistic nano-refinement under friction or stress. It has strong toughness, strong resistance to pitting corrosion, and excellent resistance to abrasion coupling damage in seawater environment. It is suitable for the protection of surface wear, corrosion, or abrasion coupling damage of underwater transmission mechanisms in marine equipment.

[0139] All aspects, embodiments, features, and examples of this invention should be considered illustrative and used to explain and illustrate the invention, but not to limit the invention. The scope of the invention is defined only by the claims.

[0140] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims.

Claims

1. A multi-principal-element alloy material with a close-packed lattice core-shell structure, characterized in that: The elemental composition of the multi-principal element alloy material satisfies Al a Co b Cr c Fe d Ni e Nb f Ti g a, b, c, d, e, f, g represent the molar ratios of the elements, where 0.01≤a≤0.3, 0.5≤b≤1.2, 0.5≤c≤1.2, 0.5≤d≤1.2, 0.5≤e≤1, 0.2≤f≤0.5, and 0.1≤g≤0.

5. The multi-principal element alloy material has a dual-phase core-shell structure, which includes an FCC structure solid solution cell core and an HCP structure shell, with the shell having a volume fraction of 8% to 20%; the core and shell are heterogeneous two phases, and both phases have a close-packed lattice. The core and shell are coordinated and distributed with high corrosion-resistant elements, including: the core is enriched with a first high corrosion-resistant element, which includes Cr; the shell is enriched with a second high corrosion-resistant element, which includes Nb and Ti.

2. The close-packed lattice core-shell structure multi-principal element alloy material according to claim 1, characterized in that: The atomic percentage of Cr enriched in the core is 16% to 25%; And / or, the atomic percentage content of Nb enriched in the shell is 5%~16%, and the atomic percentage content of Ti is 5%~16%; And / or, the atomic percentage of Cr in the shell is 10%~14%; And / or, the atomic percentage content of Nb in the core is 0.3%~4%, and the atomic percentage content of Ti is 0.3%~4%.

3. The close-packed lattice core-shell structure multi-principal element alloy material according to claim 1, characterized in that: The diameter of the core is 5μm to 50μm.

4. The close-packed lattice core-shell structured multi-principal element alloy material according to any one of claims 1-3, characterized in that: The self-corrosion current density of the densely packed lattice core-shell structured multi-principal element alloy material in seawater environment reaches 10. -8 A / cm -2 The pitting potential of this electrode relative to a saturated calomel electrode is above 1000 mV, and the wear rate is 5 × 10⁻⁶ mV. -6 mm 3 / N·m and below.

5. An anti-abrasion coating, characterized in that, Includes the close-packed lattice core-shell structure multi-principal element alloy material as described in any one of claims 1-4.

6. An anti-abrasion structure, comprising a substrate and a coating structure bonded to the substrate, characterized in that, The coating structure includes the anti-abrasion coating as described in claim 5.

7. A method for preparing an anti-abrasion structure, characterized in that, include: Provide a multi-principal component powder material, wherein the elements contained in the multi-principal component powder material satisfy Al a Co b Cr c Fe d Ni e Nb f Ti g a, b, c, d, e, f, g represent the molar ratios of the elements, where 0.01≤a≤0.3, 0.5≤b≤1.2, 0.5≤c≤1.2, 0.5≤d≤1.2, 0.5≤e≤1, 0.2≤f≤0.5, and 0.1≤g≤0.

5. The multi-principal element powder material is clad onto a substrate using laser cladding technology to form an anti-abrasion coating with a densely packed lattice core-shell structure, thereby obtaining the anti-abrasion structure. The process conditions of the laser cladding technology include: laser power of 600 W to 900 W, spot diameter of 1 mm to 1.5 mm, scanning speed of 9 mm / s to 11 mm / s, overlap rate of 40% to 60%, powder feeding speed of 11 r / min to 13 r / min, and protective gas flow rate of 13 L / min to 16 L / min.

8. The method for preparing the anti-wear structure according to claim 7, characterized in that, Specifically, it includes: The substrate is preheated to 250°C to 450°C, and then cladding is performed on the preheated substrate.

9. The method for preparing the anti-wear structure according to claim 7, characterized in that: The multi-principal component powder material is prepared by mixing elemental powders and / or by gas-atomized alloy powders.

10. The method for preparing the anti-wear structure according to claim 7, characterized in that: The powder size of the multi-principal component powder material is 45μm~150μm.

11. The method for preparing the anti-wear structure according to claim 7, characterized in that: The material of the substrate includes one or a combination of stainless steel and high-strength martensitic steel.

12. An anti-wear structure, characterized in that: It is prepared by the method of any one of claims 7-11 for the preparation of the anti-abrasion structure.

13. A transmission component for marine equipment, characterized in that, Includes the anti-abrasion structure as described in claim 6 or 12.

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