CN111058076B - Zr-based high-entropy alloy material and method for synthesizing porous spherical structure on surface of Zr-based high-entropy alloy - Google Patents

Zr-based high-entropy alloy material and method for synthesizing porous spherical structure on surface of Zr-based high-entropy alloy Download PDF

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CN111058076B
CN111058076B CN201911393681.1A CN201911393681A CN111058076B CN 111058076 B CN111058076 B CN 111058076B CN 201911393681 A CN201911393681 A CN 201911393681A CN 111058076 B CN111058076 B CN 111058076B
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entropy alloy
porous spherical
alloy
anode
anodic oxidation
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何世伟
吴天益
孙利
樊友奇
肖赛君
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Anhui University of Technology AHUT
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/10Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25F3/00Electrolytic etching or polishing
    • C25F3/02Etching
    • C25F3/08Etching of refractory metals

Abstract

The invention provides a Zr-based high-entropy alloy material and a method for synthesizing a porous spherical structure on the surface of the Zr-based high-entropy alloy material, and belongs to the technical field of metal surface treatment. The surface of the Zr-based high-entropy alloy material is provided with a porous spherical structure, and the diameter of the spherical structure is 2-5 mu m; the preparation method comprises the following steps: the method of selective dissolution and anodic oxidation is adopted, and the conditions for controlling the selective dissolution are as follows: HNO3The concentration is as follows: 25-35 wt%, time: 1-1.5 h, current: 0.5 to 1.5mA/cm2Temperature: 65-70 ℃; in the anodic oxidation process, the Zr-based high-entropy alloy after selective dissolution is used as an anode, the inert electrode is used as a cathode, and the time is as follows: 25-30 min, current: 7 to 9mA/cm2Temperature: at 20-25 ℃, the anion of the electrolyte is FAnd SO4 2‑The proportion range is as follows: 1: (10 to 11), FThe concentration is 8-10 g/L.

Description

Zr-based high-entropy alloy material and method for synthesizing porous spherical structure on surface of Zr-based high-entropy alloy
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a Zr-based high-entropy alloy material and a method for synthesizing a porous spherical structure on the surface of the Zr-based high-entropy alloy.
Background
The high-entropy alloy is a high-chaos metastable alloy material synthesized by five or more metal elements, is generally obtained by a rapid cooling method, and can retain the high-entropy characteristic in a liquid phase to the maximum extent to form an amorphous state or an alloy containing nano crystals. The zirconium-based high-entropy alloy is a high-entropy alloy taking Zr as a main element, wherein copper in the high-entropy alloy is a key for forming the Zr-based high-entropy alloy, and the high-entropy alloy is difficult to form by a rapid cooling method without copper.
Compared with the traditional titanium alloy of the artificial bone implant, the Zr-based high-entropy alloy has the elastic modulus which is closer to that of human bones, can effectively reduce stress shielding of natural bones after implantation, has higher strength and hardness, and has higher potential value in the field of implant materials. However, the untreated surface of the zirconium-based high-entropy alloy is biologically inert and cannot realize osseous connection easily. Therefore, the surface of the zirconium-based high-entropy alloy needs to be treated so as to improve the bioactivity of the zirconium-based high-entropy alloy. It is currently believed that the porous surface structure can effectively improve the bioactivity of the matrix material.
Through search, the Chinese patent application numbers are: CN201110179302.6, published date: 2013, 1 month and 2 days, discloses a zirconium-based amorphous alloy composite material, which comprises a zirconium-based amorphous alloy matrix, wherein the composite material also comprises a ceramic film layer attached to the surface of the zirconium-based amorphous alloy matrix, and the ceramic film layer contains ZrO2. The invention also provides a preparation method of the zirconium-based amorphous alloy composite material. According to the preparation method of the zirconium-based amorphous alloy composite material provided by the invention, a ceramic film layer with excellent performance can be formed on a zirconium-based amorphous alloy matrix, the ceramic film layer has high hardness, good corrosion resistance and wear resistance, and good adhesion with the zirconium-based amorphous alloy matrix, and the obtained zirconium-based amorphous alloy composite material has better amorphous alloy performance, surface decoration and protection performance, so that the application range of the zirconium-based amorphous alloy is wider, but the process adopts a plasma oxidation method, the required energy is high, the cost is high, and the method can only obtain a common compact ceramic film and cannot obtain a surface film layer with a porous structure.
For another example, the chinese patent application nos.: CN201910150899.8, published date: 19/4/2019, a method for preparing a frosted surface on a Zr-based bulk amorphous alloy is disclosed, which specifically comprises the following steps: putting the zirconium-based amorphous alloy into an electrolytic tank filled with electrolyte, and performing electro-corrosion under the constant current condition by taking the zirconium-based amorphous alloy as an anode and a graphite plate or a platinum sheet as a cathode; the electrolyte contains fluoride salt, the content of Zr element in the zirconium-based amorphous alloy is more than 50%, and other elements are 3-4 of Cu, Ni, Ti, Al and Be. The invention can prepare the frosted oxide film with compact structure, uniform frosting and light gray on the zirconium-based amorphous alloy in an electro-corrosion mode. However, the surface structure obtained by the method is a compact structure rather than a porous structure, meanwhile, the processed matrix material is amorphous alloy, and the cooling rate and the element components in the preparation process are different from those of the high-entropy alloy.
Therefore, the applicant has continuously sought a method and a material for making the zirconium-based high-entropy alloy have bioactivity, which are problems to be solved in the field of metal surface treatment at present.
Disclosure of Invention
1. Problems to be solved
The invention provides a Zr-based high-entropy alloy material, aiming at synthesizing a porous spherical structure on the surface of an alloy.
Aiming at the problem of surface biological inertia of the existing Zr-based high-entropy alloy, the invention provides a method for synthesizing a porous spherical structure on the surface of the Zr-based high-entropy alloy.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the surface of the Zr-based high-entropy alloy material is provided with a porous spherical structure.
Further, the metal elements in the Zr-based high-entropy alloy include, but are not limited to, Zr, Al, Cu, Ti and Fe.
Further, the porous spherical structure has ZrO as a main component2
Further, the diameter of the porous spherical structure is 2-5 μm.
A method for synthesizing a porous spherical structure on the surface of a Zr-based high-entropy alloy comprises the steps of selectively dissolving Cu on the surface of the Zr-based high-entropy alloy in the Zr-based high-entropy alloy, and then using the Zr-based high-entropy alloy to synthesize a porous spherical structureThe Zr-based high-entropy alloy after selective dissolution is used as an anode to carry out an anodic oxidation process on the surface of the Zr-based high-entropy alloy to form a porous spherical structure, wherein the main component of the porous spherical structure is ZrO2
Further, the metal elements in the Zr-based high-entropy alloy before selective dissolution include, but are not limited to, five elements of Zr, Al, Cu, Ti, and Fe, and are a Zr-based high-entropy alloy prepared by a rapid cooling method after a master alloy is formed at a high temperature, wherein the mass fractions of the metal elements in the Zr-based high-entropy alloy before selective dissolution are Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent.
Further, the selective dissolving process is electrochemical selective dissolving, wherein nitric acid is selected as an electrolyte in the electrochemical selective dissolving process, the Zr-based high-entropy alloy is used as an anode, and the inert electrode is used as a cathode.
Further, the concentration of the nitric acid is 25-35 wt%, and the inert electrode is graphite or platinum; the current density of the electrochemical selective dissolution is 0.5-1.5 mA/cm2The time is 1-1.5 h, the temperature of the electrolyte is 65-70 ℃, wherein the chemical reaction equation in the electrochemical selective dissolution process is as follows: anode: cu-2e-=Cu2+And a cathode: 2H++2e-=H2↑。
Further, the anodic oxidation process is electrochemical anodic oxidation, wherein anions in the electrolyte of the electrochemical anodic oxidation comprise F-And SO4 2-The cation comprises Na+、NH4 +、K+One or two of them; the electrochemical anodic oxidation takes the Zr-based high-entropy alloy after selective dissolution as an anode and an inert electrode as a cathode, wherein the main electrochemical reaction equation in the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2
Further, F in the electrolyte of the electrochemical anodic oxidation-And SO4 2-The concentration ratio of (1): (10-11) in which F-The concentration of (b) is 8-10 g/L.
Further, the electricityThe inert electrode for chemical anode oxidation is graphite or platinum; the current density of the electrochemical anodic oxidation is 7-9 mA/cm2The time is 25-30 min, and the temperature of the electrolyte is 20-25 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention can synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, and is worth explaining that the structure formed on the surface of the Zr-based high-entropy alloy is not a common porous structure, but a porous spherical structure, the key of forming the structure is that copper on the surface of the structure is selectively dissolved firstly, then the structure is anodized to form oxide, the electrolyte formula and condition control in the two steps are optimized, a method combining the two steps is adopted, rather than directly using a Zr-based high-entropy alloy containing no copper, because copper is the key to forming the Zr-based high-entropy alloy, the high-entropy alloy is difficult to form by a rapid cooling method without copper, however, the existence of copper can consume current in the later anodic oxidation process and influence the anodic oxidation to form a porous spherical structure, so that the two steps are combined, and the formation of the porous spherical structure on the surface of the Zr-based high-entropy alloy is facilitated;
(2) the main component of the porous spherical structure synthesized on the surface of the Zr-based high-entropy alloy is ZrO2After 7 days of mineralization in simulated body fluid (SBF solution), compared with Zr-based high-entropy alloy without surface treatment, hydroxyapatite structure is easier to form, so that the Zr-based high-entropy alloy with the porous spherical structure synthesized on the surface can improve the bioactivity of the material;
(3) the selective dissolving process is electrochemical selective dissolving, mainly dissolves copper, and dissolves copper on the surface of the Zr-based high-entropy alloy electrode, wherein HNO with the concentration of 25-35 wt% is selected3For the electrolyte, Al and Fe may only be passivated in concentrated nitric acid without applying electricity, the oxidation potential of Al and Fe increases after applying a positive potential, and passivation in nitric acid of this concentration is possible, and according to experimental results, Fe is still slightly dissolved out, but the amount is less and not as much as copper is negligible, so that it can be considered that 25 is the valueWithin the concentration range of nitric acid of 35 wt%, only Cu can be selectively dissolved, and other elements can be passivated, so that metal aluminum and iron which are active in the Zr-based high-entropy alloy compared with copper are passivated in the nitric acid with the concentration, copper on the surface of an anode is mainly gradually dissolved, and specific conditions such as current density, temperature and the like are controlled, so that the copper on the surface of the Zr-based high-entropy alloy can not be dissolved in the Zr-based high-entropy alloy within 1-1.5 h, the copper on the surface of the Zr-based high-entropy alloy can be well removed, and the interference of the copper in the later-stage anodic oxidation film forming process is avoided;
(4) according to the invention, the electrochemical anodic oxidation is adopted to treat the decoppered Zr-based high-entropy alloy, the decoppered Zr-based high-entropy alloy can effectively reduce the current generated by copper dissolution in the anodic oxidation process, the oxidation potential is improved, the film formation of the main metal Zr is further promoted, and the main component formed on the surface of the Zr-based high-entropy alloy is ZrO2The porous spherical structure of (1).
Drawings
FIG. 1 is a scanning electron micrograph (5000 times) of a porous spherical structure synthesized on the surface of the Zr-based high-entropy alloy in example 1;
FIG. 2 is a scanning electron micrograph (10000 times) of a porous spherical structure synthesized on the surface of the Zr-based high-entropy alloy in example 1;
FIG. 3 is an energy spectrum of the Zr-based high-entropy alloy having formed porous spherical structures in example 1 after 7 days of mineralization in SBF;
FIG. 4 is an energy spectrum of the Zr-based high-entropy alloy having formed porous spherical structures in example 2 after 7 days of mineralization in SBF;
FIG. 5 is an energy spectrum of the Zr-based high-entropy alloy having formed porous spherical structures in example 3 after 7 days of mineralization in SBF;
FIG. 6 is an energy spectrum of the Zr-based high-entropy alloy having formed porous spherical structures in example 4 after 7 days of mineralization in SBF;
FIG. 7 is an energy spectrum of the Zr-based high-entropy alloy having formed the porous spherical structure in example 5 after 7 days of mineralization in SBF.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy comprises the following steps:
(1) selecting Zr-based high-entropy alloy: the Zr-based high-entropy alloy is prepared by adopting a method of forming a master alloy at a high temperature and then rapidly cooling, wherein the mass fractions of metal elements of the Zr-based high-entropy alloy are respectively Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent;
(2) selective dissolution: taking the Zr-based high-entropy alloy in the step (1) as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in HNO with the concentration of 25 wt%3In the electrolyte solution, the temperature of the electrolyte solution is 65 ℃, and the current density is 1mA/cm2And under the condition that the electrolysis time is 1h, connecting the anode and the cathode with a power supply to form a circuit loop, and selectively dissolving the copper on the surface of the alloy, wherein the electrode reaction equation of the anode and the cathode is as follows: anode: cu-2e-=Cu2+And the cathode: 2H++2e-=H2↑;
(3) Anodic oxidation: taking the Zr-based high-entropy alloy selectively dissolved in the step (2) as an anode and a platinum sheet as a cathode, placing the anode and the cathode in an electrolyte, and controlling the temperature of the electrolyte to be 20 ℃ and the current density to be 7mA/cm2Connecting the anode and the cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 25min, and carrying out anodic oxidation to synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, wherein the main component of the porous spherical structure is ZrO2Namely, the main electrochemical reaction equation of the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2Other components also comprise a small amount of oxides such as aluminum oxide, iron oxide, titanium oxide and the like; obtaining the Zr-based high-entropy alloy material of the embodiment;
it is worth noting that the electrolyte selection during anodization is related to whether the porous spherical structure is primarily ZrO or not2After many studies and experiments, the inventors found that the electrolyte of the present embodiment should have an anion F-And SO4 2-And F is-And SO4 2-In a concentration ratio of 1:10, F-Concentration ofIs 8g/L, the cation is Na+
As shown in fig. 1 and fig. 2, SEM spectra of the Zr-based high-entropy alloy material obtained in this embodiment after being enlarged by 5000 times and 10000 times under a scanning electron microscope are shown, it is obvious that dense porous spherical structures are synthesized on the surface of the Zr-based high-entropy alloy material in this embodiment, and through tests, the diameter of the porous spherical structures is between 2 μm and 5 μm.
In order to clearly compare the compositions of the elements in the Zr-based high-entropy alloy before and after selective dissolution and before and after anodization, the mass fractions of the elements in the Zr-based high-entropy alloy before and after selective dissolution and after anodization are shown in table 1.
TABLE 1 EXAMPLE 1 Mass fractions of respective elements in Zr-based high-entropy alloy in respective stages
Element (wt%) Zr Al Cu Ti Fe O
Initial alloy (wt%) 55 10 15 10 10 0
After selective dissolution (wt%) 62.8 11.4 4.3 11.9 9.6 0
After anodic oxidation (wt%) 45.8 8.1 3.1 8.3 6.5 28.2
Example 2
The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy comprises the following steps:
(1) selecting Zr-based high-entropy alloy: the Zr-based high-entropy alloy is prepared by adopting a method of forming a master alloy at a high temperature and then rapidly cooling, wherein the mass fractions of metal elements of the Zr-based high-entropy alloy are respectively Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent;
(2) selective dissolution: taking the Zr-based high-entropy alloy in the step (1) as an anode and graphite as a cathode, and placing the anode and the cathode in HNO with the concentration of 30 wt%3In the electrolyte solution, the temperature of the electrolyte solution is 65 ℃, and the current density is 0.5mA/cm2And connecting the anode and the cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 75min, and selectively dissolving the copper on the surface of the alloy, wherein the electrode reaction equation of the anode and the cathode is as follows: anode: cu-2e-=Cu2+And the cathode: 2H++2e-=H2↑;
(3) Anodic oxidation: taking the Zr-based high-entropy alloy selectively dissolved in the step (2) as an anode and graphite as a cathode, placing the anode and the cathode in electrolyte, and controlling the temperature of the electrolyte at 25 ℃ and the current density at 7mA/cm2And connecting an anode and a cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 27min, carrying out anodic oxidation to synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, wherein the porous spherical structure has the diameter of 2-5 mu m and mainly comprises ZrO through testing2Namely, the main electrochemical reaction equation of the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2Other components also comprise a small amount of oxides such as aluminum oxide, iron oxide, titanium oxide and the like; obtaining the Zr-based high-entropy alloy material of the embodiment;
it is worth noting that the electrolyte selection during anodization is related to whether the porous spherical structure is primarily ZrO or not2After many studies and experiments, the inventors found that the electrolyte of the present embodiment should have an anion F-And SO4 2-And F is-And SO4 2-In a concentration ratio of 1:10.5, F-The concentration is 8g/L, the cation is Na+And NH4 +
Example 3
The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy comprises the following steps:
(1) selecting Zr-based high-entropy alloy: the Zr-based high-entropy alloy is prepared by adopting a method of forming a master alloy at a high temperature and then rapidly cooling, wherein the mass fractions of metal elements of the Zr-based high-entropy alloy are respectively Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent;
(2) selective dissolution: taking the Zr-based high-entropy alloy in the step (1) as an anode and graphite as a cathode, and placing the anode and the cathode in HNO with the concentration of 30 wt%3In the electrolyte solution, the temperature of the electrolyte solution is 70 ℃, and the current density is 1.5mA/cm2And connecting the anode and the cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 1.5h, and selectively dissolving the copper on the surface of the alloy and the copper on the anode and the cathodeThe electrode reaction equation is: anode: cu-2e-=Cu2+And the cathode: 2H++2e-=H2↑;
(3) Anodic oxidation: taking the Zr-based high-entropy alloy selectively dissolved in the step (2) as an anode and graphite as a cathode, placing the anode and the cathode in electrolyte, and controlling the temperature of the electrolyte to be 25 ℃ and the current density to be 8mA/cm2And connecting an anode and a cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 27min, carrying out anodic oxidation to synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, wherein the porous spherical structure has the diameter of 2-5 mu m and mainly comprises ZrO through testing2Namely, the main electrochemical reaction equation of the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2Other components also comprise a small amount of oxides such as aluminum oxide, iron oxide, titanium oxide and the like; obtaining the Zr-based high-entropy alloy material of the embodiment;
it is worth noting that the electrolyte selection during anodization is related to whether the porous spherical structure is primarily ZrO or not2After many studies and experiments, the inventors found that the electrolyte of the present embodiment should have an anion F-And SO4 2-And F is-And SO4 2-In a concentration ratio of 1:11, F-The concentration is 8g/L, the cation is Na+And K+
Example 4
The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy comprises the following steps:
(1) selecting Zr-based high-entropy alloy: the Zr-based high-entropy alloy is prepared by adopting a method of forming a master alloy at a high temperature and then rapidly cooling, wherein the mass fractions of metal elements of the Zr-based high-entropy alloy are respectively Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent;
(2) selective dissolution: taking the Zr-based high-entropy alloy in the step (1) as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in HNO with the concentration of 35 wt%3In the electrolyte solution, the temperature of the electrolyte solution is 70 ℃, and the current density is 1mA/cm2Electrolyzing for 1.5hThe anode and the cathode are connected with a power supply to form a circuit loop, copper on the surface of the alloy is selectively dissolved, and the electrode reaction equation of the anode and the cathode is as follows: anode: cu-2e-=Cu2+And the cathode: 2H++2e-=H2↑;
(3) Anodic oxidation: taking the Zr-based high-entropy alloy selectively dissolved in the step (2) as an anode and a platinum sheet as a cathode, placing the anode and the cathode in electrolyte, and controlling the temperature of the electrolyte to be 25 ℃ and the current density to be 7mA/cm2And connecting an anode and a cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 30min, carrying out anodic oxidation to synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, wherein the porous spherical structure has the diameter of 2-5 mu m and mainly comprises ZrO through testing2Namely, the main electrochemical reaction equation of the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2Other components also comprise a small amount of oxides such as aluminum oxide, iron oxide, titanium oxide and the like; obtaining the Zr-based high-entropy alloy material of the embodiment;
it is worth noting that the electrolyte selection during anodization is related to whether the porous spherical structure is primarily ZrO or not2After many studies and experiments, the inventors found that the electrolyte of the present embodiment should have an anion F-And SO4 2-And F is-And SO4 2-In a concentration ratio of 1:10, F-The concentration is 9g/L, the cation is K+、NH4 +
Example 5
The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy comprises the following steps:
(1) selecting Zr-based high-entropy alloy: the Zr-based high-entropy alloy is prepared by adopting a method of forming a master alloy at a high temperature and then rapidly cooling, wherein the mass fractions of metal elements of the Zr-based high-entropy alloy are respectively Zr: 55%, Al: 10%, Cu: 15%, Ti: 10%, Fe: 10 percent;
(2) selective dissolution: taking the Zr-based high-entropy alloy in the step (1) as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in HNO with the concentration of 35 wt%3Solutions ofIn the electrolyte solution (2), the temperature of the electrolyte solution is 70 ℃, and the current density is 1mA/cm2And under the condition that the electrolysis time is 1.5h, connecting the anode and the cathode with a power supply to form a circuit loop, and selectively dissolving the copper on the surface of the alloy, wherein the electrode reaction equation of the anode and the cathode is as follows: anode: cu-2e-=Cu2+And the cathode: 2H++2e-=H2↑;
(3) Anodic oxidation: taking the Zr-based high-entropy alloy selectively dissolved in the step (2) as an anode and a platinum sheet as a cathode, placing the anode and the cathode in electrolyte, and controlling the temperature of the electrolyte to be 25 ℃ and the current density to be 9mA/cm2And connecting an anode and a cathode with a power supply to form a circuit loop under the condition that the electrolysis time is 30min, carrying out anodic oxidation to synthesize a porous spherical structure on the surface of the Zr-based high-entropy alloy, wherein the porous spherical structure has the diameter of 2-5 mu m and mainly comprises ZrO through testing2Namely, the main electrochemical reaction equation of the anodic oxidation process is as follows: zr +2[ O ]]=ZrO2Other components also comprise a small amount of oxides such as aluminum oxide, iron oxide, titanium oxide and the like; obtaining the Zr-based high-entropy alloy material of the embodiment;
it is worth noting that the electrolyte selection during anodization is related to whether the porous spherical structure is primarily ZrO or not2After many studies and experiments, the inventors found that the electrolyte of the present embodiment should have an anion F-And SO4 2-And F is-And SO4 2-In a concentration ratio of 1:11, F-The concentration is 10g/L, the cation is NH4 +
Performance testing
In order to prove that the Zr-based high-entropy alloy materials prepared in the embodiments 1 to 5 have good bioactivity, the Zr-based high-entropy alloy materials of the five embodiments are subjected to an experiment of the capability of forming apatite on the surface of the material in a human Simulated Body Fluid (SBF) to react the bioactivity of the material in vivo. After 7 days of mineralization in SBF, the energy spectrum diagrams of the Zr-based high-entropy alloy materials prepared in examples 1 to 5 are shown in FIGS. 3 to 7, the corresponding element contents are shown in Table 2, and the element contents corresponding to the energy spectrum of the untreated Zr-based high-entropy alloy are shown in Table 3.
TABLE 2 element contents corresponding to energy spectra of Zr-based high-entropy alloy materials obtained in examples 1 to 5 after 7 days of mineralization in SBF
TABLE 3 element content corresponding to energy spectrum of untreated Zr-based high entropy alloy after 7 days of mineralization in SBF
As can be seen from the data in fig. 3 to 7 and tables 2 and 3, in examples 1 to 5, after the Zr-based high-entropy alloy having a porous spherical structure formed by the "electro-corrosion-electro-oxidation" treatment is mineralized in a simulated body fluid (SBF solution) for 7 days, the Ca/P atomic ratios at five points on the surface are respectively: 1.51, 1.72, 1.61, 1.53 and 1.48, which are close to the Ca/P atomic ratio (1.67) in hydroxyapatite (HAp) desired to be obtained on the surface. The surface of the Zr-based amorphous alloy after being dealloyed is formed with a hydroxyapatite layer covering the surface of the matrix after being mineralized in vitro by simulated body fluid for 7 days. As can be seen from Table 3, the untreated Zr-based high-entropy alloy had a Ca/P atomic ratio of 4.76 on the surface thereof after 7 days of mineralization in the SBF solution, which was very different from the Ca/P atomic ratio (1.67) of hydroxyapatite (HAp). The Zr-based high-entropy alloy with the porous spherical structure formed on the surface after the electro-corrosion-electro-oxidation treatment is considered to be easier to form a hydroxyapatite structure in an experiment for simulating in-vitro mineralization of body fluid, so that the biomineralization activity of the Zr-based high-entropy alloy is obviously improved compared with that before the treatment.
The examples described herein are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. A Zr-based high-entropy alloy material is characterized in that: the surface of the Zr-based high-entropy alloy material is provided with a porous spherical structure, wherein the main component of the porous spherical structure is ZrO2
2. The Zr-based high-entropy alloy material according to claim 1, wherein: the metal elements in the Zr-based high-entropy alloy comprise five elements of Zr, Al, Cu, Ti and Fe.
3. The Zr-based high-entropy alloy material according to claim 1, wherein: the diameter of the porous spherical structure is 2-5 mu m.
4. A method for synthesizing a porous spherical structure on the surface of a Zr-based high-entropy alloy, wherein the Zr-based high-entropy alloy contains Zr and Cu, and is characterized in that: firstly, selectively dissolving Cu on the surface of the Zr-based high-entropy alloy, and then carrying out an anodic oxidation process on the surface of the Zr-based high-entropy alloy by taking the selectively dissolved Zr-based high-entropy alloy as an anode to form a porous spherical structure, wherein the main component of the porous spherical structure is ZrO2(ii) a The selective dissolving process is electrochemical selective dissolving, wherein nitric acid is selected as an electrolyte in the electrochemical selective dissolving process, a Zr-based high-entropy alloy is used as an anode, an inert electrode is used as a cathode, the concentration of the nitric acid is 25-35 wt%, and the current density of the electrochemical selective dissolving process is 0.5-1.5 mA/cm2The time is 1-1.5 h, and the temperature of the electrolyte is 65-70 ℃.
5. The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy according to claim 4, wherein the method comprises the following steps: the inert electrode is graphite or platinum.
6. The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy according to claim 4, wherein the method comprises the following steps: the anodic oxidation process is electrochemical anodic oxidation, wherein anions in the electrolyte of the electrochemical anodic oxidation comprise F-And SO4 2-The cation comprises Na+、NH4 +、K+One or two of them; the electrochemical anodic oxidation takes the Zr-based high-entropy alloy after selective dissolution as an anode and an inert electrode as a cathode.
7. The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy according to claim 6, wherein the method comprises the following steps: f in the electrolyte of the electrochemical anodic oxidation-And SO4 2-The concentration ratio of (1): (10-11) in which F-The concentration of (b) is 8-10 g/L.
8. The method for synthesizing the porous spherical structure on the surface of the Zr-based high-entropy alloy according to claim 6, wherein the method comprises the following steps: the inert electrode for electrochemical anodization is graphite or platinum; the current density of the electrochemical anodic oxidation is 7-9 mA/cm2The time is 25-30 min, and the temperature of the electrolyte is 20-25 ℃.
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