CN115852229A - Acid corrosion resistant rare earth high-entropy alloy and preparation method thereof - Google Patents
Acid corrosion resistant rare earth high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr a NiCu 0.5 Ti 0.5 RE x Wherein RE comprises any one or combination of at least two of Sm, gd, Y or Ho; by doping rare earth elements, the grain boundary can be purified, and the alloy structure can be improved. The preparation method comprises the following steps: alloy raw materials are weighed according to the molar ratio, and then vacuum melting, annealing and constant potential passivation are sequentially carried out to obtain the rare earth high-entropy alloy. The preparation method is simple, can realize industrial production, and can effectively improve the alloy structure and greatly improve the passivation by combining the treatment of smelting, annealing and constant potential passivationThe method has the advantages of reducing the density of passivation current, enhancing the corrosion resistance of the surface of the high-entropy alloy and prolonging the service life of the high-entropy alloy material.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloys, and particularly relates to an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof.
Background
High-entropy alloy has received increasing attention in various fields as a material having unique physical and chemical properties. Particularly, the high-entropy alloy can be used as a self-supporting integrated electrode due to the excellent mechanical property, so that the defect that the powder nano material can be combined with a substrate only by adding an adhesive is overcome, and the conductivity is enhanced.
In recent years, the preparation method of the high-entropy alloy mainly comprises vacuum melting, sintering and other methods. CN108642362A discloses a high-entropy alloy and a preparation method thereof, wherein the elements in the high-entropy alloy are Cr, fe, co, ni and Ta with unequal atomic ratios; the preparation method comprises the following steps: and putting the weighed raw materials into an electric arc melting furnace for melting to obtain the high-entropy alloy.
CN114686717A discloses a preparation method of a high entropy alloy, comprising: (1) Pressing and sintering the high-entropy alloy element powder to obtain a high-entropy alloy block primary product; (2) And (2) deoxidizing the high-entropy alloy block primary product obtained in the step (1), cooling to obtain the high-entropy alloy block, mixing the high-entropy alloy block primary product with sufficient deoxidizing metal and fluxing agent, and then carrying out heat preservation treatment in an atmosphere furnace.
High entropy alloys have a variety of principal elements, the constituent elements of which are complex but generally have a simple phase structure, such as cocrfermni high entropy alloys, which were first explored in 2004 by Cantor et al, have a single phase FCC (face centered cubic) crystal structure, exhibit high ductility, excellent electrical resistance under irradiation and good mechanical properties at low temperatures, but are very low in yield strength due to their high cost. Another representative structure of the high-entropy alloy is a BBC (body centered cubic) structure, which is a material having low plasticity but high strength. Although the high-entropy alloy composed of FCC + BCC biphase has better strength and plasticity, the multiphase alloy has phase potential difference, and interphase corrosion easily occurs in a solution environment.
Therefore, the development of a high-entropy alloy which can improve the interphase corrosion of the multiphase high-entropy alloy and enhance the corrosion resistance is needed.
Disclosure of Invention
The invention aims to provide an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, which solve the problem that a multiphase alloy is easy to generate interphase corrosion and simultaneously improve the corrosion resistance of the high-entropy alloy in an acid solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an acid corrosion resistant rare earth high-entropy alloy, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 RE x Wherein RE comprises any one or a combination of at least two of Sm, gd, Y or Ho, typical but non-limiting examples of which are: combinations of Sm and Gd, combinations of Y and Ho or combinations of Sm and Y, and the like.
The molar ratio of Cr in the rare earth high-entropy alloy is 0.3. Ltoreq. A.ltoreq.1.2, and may be, for example, 0.3, 0.5, 0.7, 0.9, 1, 1.1 or 1.2, but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and 0.7 is preferable.
The molar ratio of RE in the rare earth high-entropy alloy is 0.01 ≦ x ≦ 0.3, and may be, for example, 0.01, 0.03, 0.05, 0.07, 0.1, 0.15, 0.2, 0.25, or 0.3, but is not limited to the values listed, and other values not listed in the numerical range may be similarly applied.
According to the invention, by doping rare earth elements, the crystal boundary can be purified, the alloy structure is improved, and the oxidation of the surface of a sample is facilitated through the oxygen affinity of the alloy, so that a compact oxide film is generated, and the continuous dissolution of the alloy is prevented; under the acid environment, the rare earth high-entropy alloy has better corrosion resistance.
As a preferable technical scheme of the invention, the structure of the rare earth high-entropy alloy is FCC phase, BCC phase and intermetallic compound.
Preferably, the intermetallic compounds (IMs) precipitate on the surface of the FCC phase.
In the invention, IMs are separated from FCC on the surface of FCC, and have the function of improving intergranular corrosion.
As the preferable technical scheme of the invention, the rare earth high-entropy alloy is less than or equal to 1mol/L H 2 SO 4 In the passivation current density of less than 1 x 10 -3 A/cm 2 For example, it may be 1 × 10 -4 A/cm 2 、0.9×10 -4 A/cm 2 、0.8×10 -4 A/cm 2 、0.5×10 - 4 A/cm 2 Or 0.3X 10 -4 A/cm 2 And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
In a second aspect, the invention provides a preparation method of the rare earth high-entropy alloy, which comprises the following steps: and sequentially carrying out vacuum melting, annealing and constant potential passivation on the alloy raw materials according to the molar ratio to obtain the rare earth high-entropy alloy.
The invention combines smelting, annealing and constant potential passivation, can effectively improve alloy structure, greatly improve passivation effect, reduce passivation current density, enhance corrosion resistance of the surface of the high-entropy alloy, and simultaneously precipitate Ni 3 Ti covers the surface of FCC, so that interphase corrosion can be effectively prevented, and the service life of the high-entropy alloy material is prolonged; meanwhile, a passivation film generated on the surface of the alloy is expected to replace electroplating, so that high toxicity of electroplating electrolyte is avoided.
As a preferred technical solution of the present invention, the vacuum melting is: and melting the Ti block, and then melting other alloy blocks to obtain the button ingot alloy.
In the invention, the raw materials (excluding rare earth alloy blocks) are cleaned before vacuum melting, and the cleaning comprises the steps of pickling in 0.5mol/L HCl solution for 30s in sequence, then heating to remove HCl, and then carrying out ethanol ultrasonic treatment and drying.
Preferably, the vacuum degree of the vacuum melting is less than 7 x 10 -3 MPa, for example, may be 5X 10 -3 MPa、3×10 - 3 MPa、1×10 -3 MPa、9×10 -4 MPa、7×10 -4 MPa or 1X 10 -4 MPa, etc., but is not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the number of times of vacuum melting is 4 or more, for example, 4, 5, 6, 7 or 8 times, but not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 4 to 6 times.
In the invention, the melting needs to be turned over each time.
As a preferred embodiment of the present invention, the annealing is performed in a protective atmosphere.
Preferably, the protective atmosphere comprises argon.
Preferably, the annealing includes a first heat-retention, a first cooling, and a second cooling performed in this order.
According to the invention, the first heat-preservation annealing can promote elimination of passivation defects, slow cooling of the first cooling and rapid cooling of the second cooling are combined, and the rare earth elements can further promote oxidation.
In a preferred embodiment of the present invention, the temperature of the first heat-retaining step is 500 to 1300 ℃, and may be, for example, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or 1300 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the first heat preservation time is 6-24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the first cooling is furnace cooling.
Preferably, the final temperature of the first cooling is 380 to 450 ℃, for example 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃ or 450 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the second cooling is air cooling.
As a preferred embodiment of the present invention, the potentiostatic passivation includes: the alloy sample is made into an electrode by adopting resin, and then constant potential passivation is carried out in a three-electrode system, so that an oxide film is formed on the surface of the alloy sample.
In the present invention, the alloy sample is made into an electrode using a resin, and only the surface to be passivated is exposed.
According to the invention, constant potential passivation treatment is carried out in an acid solution, so that the surface passivation film of the high-entropy alloy can be promoted to be more compact, the passivation current density is reduced, the service life of the high-entropy alloy material is prolonged, and the acid corrosion resistance of the high-entropy alloy is further improved; the dense passive film formed after passivation can greatly reduce the current density of passivation from 1 × 10 -3 A/cm 2 Is reduced to 1 × 10 -4 A/cm 2 Greatly prolongs the service life of the passive film and is expected to replace the corrosion prevention of the electroplating coating.
Preferably, before the constant potential passivation, the annealed button ingot alloy is sequentially polished and subjected to wire cutting to obtain an alloy sample.
In the invention, the polishing is performed by using SiC sand paper to remove oxide skin on the surface.
As a preferred embodiment of the present invention, the resin includes an epoxy resin.
Preferably, the potentiostatic passivation has a potential of 0.1 to 1.0V, for example 0.1V, 0.3V, 0.5V, 0.7V, 0.9V or 1.0V, but is not limited to the values recited, and other values not recited in this range are equally applicable.
Preferably, the potentiostatic passivation is carried out for a period of time of 0.5h or more, for example 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 0.5 to 5h.
Preferably, the electrolyte of the three-electrode system is H with the concentration less than or equal to 1mol/L 2 SO 4 For example, the concentration may be 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L or 1.0mol/L, but the concentration is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The thickness of the oxide film is preferably 1.0 to 300. Mu.m, and may be, for example, 1.0. Mu.m, 50. Mu.m, 100. Mu.m, 150. Mu.m, 200. Mu.m, 250. Mu.m, or 300. Mu.m, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Vacuum melting is carried out on the alloy raw materials according to the molar ratio, a Ti block is melted firstly, and then other alloys are melted to prepare a button ingot alloy;
the vacuum degree of the vacuum melting is less than 7 multiplied by 10 -3 MPa, the smelting times are more than or equal to 4;
(2) Annealing the button ingot alloy in the step (1) in a protective atmosphere;
the annealing comprises the steps of sequentially keeping the temperature at 500-1300 ℃ for 6-24h, then cooling to 450-380 ℃ along with the furnace, and finally taking out and air cooling;
(3) Sequentially polishing and linearly cutting the annealed button ingot alloy obtained in the step (2) to obtain an alloy sample, then preparing the alloy sample into an electrode by adopting epoxy resin, and then adopting a three-electrode system to obtain H with the concentration less than or equal to 1mol/L 2 SO 4 The constant potential passivation is carried out for more than or equal to 0.5h under the potential of 0.1-1.0V, and an oxide film with the thickness of 1.0-300 mu m is formed on the surface.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention providesCorrosion-resistant FeCr a NiCu 0.5 Ti 0.5 RE x The rare earth high-entropy alloy has a wide passivation region and low passivation current density in an acid solution by doping rare earth elements;
(2) The preparation method provided by the invention sequentially combines vacuum melting, annealing and constant potential passivation, can effectively improve the alloy structure, greatly improve the passivation effect, reduce the passivation current density, enhance the corrosion resistance of the surface of the high-entropy alloy, and simultaneously precipitate Ni 3 Ti covers the surface of FCC, so that interphase corrosion can be effectively prevented, and the service life of the high-entropy alloy material is prolonged; meanwhile, a passivation film generated on the surface of the alloy is expected to replace electroplating, so that high toxicity of electroplating electrolyte is avoided.
Drawings
FIG. 1 is an XRD pattern of high entropy alloys produced by examples 1 to 5 of the present invention and comparative examples 1 to 3;
FIG. 2 is an SEM image of high-entropy alloys produced in examples 1 to 5 of the present invention and comparative examples 1 to 3;
FIG. 3 shows that the high entropy alloys obtained in examples 1 to 5 of the present invention and comparative examples 1 to 3 were 0.5mol/L H 2 SO 4 Polarization graph of (1);
FIG. 4 is an SEM image of a rare earth high-entropy alloy passivation film prepared in example 2 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The purity of the alloy raw materials used in the embodiment and the comparative example is more than or equal to 99 percent.
Example 1
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Y 0.01 ；
The preparation method comprises the following steps:
(1) Pickling the alloy raw materials except the rare earth Y in 0.5mol/L HCl solution for 30s according to the molar mass ratio, then heating to remove HCl, and then carrying out ethanol ultrasonic treatment and drying; putting the weighed raw materials into a water-cooled copper crucible for vacuum melting, firstly melting Ti blocks, and then melting other alloy blocks to prepare a button ingot alloy with the diameter of 30 mm;
the vacuum degree of the vacuum melting is pumped to 1 multiplied by 10 -3 MPa, 4 times of smelting;
(2) Annealing the button ingot alloy in the step (1) in an argon atmosphere;
the annealing comprises the steps of sequentially keeping the temperature at 800 ℃ for 12 hours, then cooling to 400 ℃ along with the furnace, and finally taking out for air cooling;
(3) Polishing the surface of the annealed button ingot alloy in the step (2) by using SiC abrasive paper, cutting the surface into small samples in a linear manner, performing coarse grinding and fine grinding on the small samples in a metallographic grinder by sequentially passing through 400-mesh, 800-mesh, 1200-mesh and 2000-mesh abrasive paper, rotating the sample by 90 degrees before replacing the abrasive paper each time, then polishing the sample by using diamond polishing paste until the sample presents a mirror surface effect to obtain an alloy sample, then manufacturing the alloy sample into an electrode by using epoxy resin, only exposing the surface to be passivated, and adopting a three-electrode system to be 0.5mol/L H 2 SO 4 In the middle process, a rare earth high-entropy alloy sample is used as a working electrode, a Pt sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, constant potential passivation is carried out for 2 hours under the potential of 0.6V, and a layer of oxide film with the thickness of 250 micrometers is formed on the surface.
Example 2
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Y 0.04 (ii) a The preparation method is the same as that of example 1;
SEM characterization results of the prepared rare earth high-entropy alloy passivation film are shown in figure 4, and a layer of compact oxidation film is formed on the surface of the rare earth high-entropy alloy.
Example 3
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Y 0.1 (ii) a The preparation method is the same as in example 1.
Example 4
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Sm 0.1 ；
The preparation method comprises the following steps:
(1) Pickling alloy raw materials except for rare earth Sm in 0.5mol/L HCl solution for 30s according to a molar mass ratio, then heating to remove HCl, and then carrying out ethanol ultrasonic treatment and drying; putting the weighed raw materials into a water-cooled copper crucible for vacuum melting, firstly melting Ti blocks, and then melting other alloy blocks to prepare a button ingot alloy with the diameter of 30 mm;
the vacuum degree of the vacuum melting is pumped to 5 multiplied by 10 -4 MPa, the smelting times are 6 times;
(2) Annealing the button ingot alloy in the step (1) in an argon atmosphere;
the annealing comprises the steps of sequentially keeping the temperature at 1000 ℃ for 12 hours, then cooling to 400 ℃ along with the furnace, and finally taking out for air cooling;
(3) Polishing the surface of the annealed button ingot alloy in the step (2) by using SiC abrasive paper, cutting the surface into small samples in a linear manner, performing coarse grinding and fine grinding on the small samples in a metallographic grinder by sequentially passing through 400-mesh, 800-mesh, 1200-mesh and 2000-mesh abrasive paper, rotating the sample by 90 degrees before changing the abrasive paper each time, polishing by using diamond polishing paste until the sample presents a mirror surface effect to obtain an alloy sample, then manufacturing the alloy sample into an electrode by adopting epoxy resin, only exposing the surface to be passivated, and adopting a three-electrode system to be 0.5mol/L H 2 SO 4 In the process, a rare earth high-entropy alloy sample is used as a working electrode, a Pt sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, constant potential passivation is carried out for 5 hours under the potential of 1.0V, and a layer of oxidation film with the thickness of 230 mu m is formed on the surface.
Example 5
This example provides an acid corrosion resistant rare earth high-entropy alloy with a chemical formula of FeCr and a preparation method thereof 0.7 NiCu 0.5 Ti 0.5 Gd 0.01 ；
The preparation method comprises the following steps:
(1) Pickling the alloy raw materials except the rare earth Gd in 0.5mol/L HCl solution for 30s according to the molar mass ratio, then heating to remove HCl, and then carrying out ethanol ultrasonic treatment and drying; putting the weighed raw materials into a water-cooled copper crucible for vacuum melting, firstly melting Ti blocks, and then melting other alloy blocks to prepare a button ingot alloy with the diameter of 30 mm;
the vacuum degree of the vacuum melting is pumped to 1 multiplied by 10 -4 MPa, 4 times of smelting;
(2) Annealing the button ingot alloy in the step (1) in an argon atmosphere;
the annealing comprises the steps of sequentially keeping the temperature at 800 ℃ for 6h, then cooling to 450 ℃ along with the furnace, and finally taking out for air cooling;
(3) Polishing the surface of the annealed button ingot alloy in the step (2) by using SiC abrasive paper, cutting the surface into small samples in a linear manner, performing coarse grinding and fine grinding on the small samples in a metallographic grinder by sequentially passing through 400-mesh, 800-mesh, 1200-mesh and 2000-mesh abrasive paper, rotating the sample by 90 degrees before changing the abrasive paper each time, polishing by using diamond polishing paste until the sample presents a mirror surface effect to obtain an alloy sample, then manufacturing the alloy sample into an electrode by adopting epoxy resin, only exposing the surface to be passivated, and adopting a three-electrode system to be 0.5mol/L H 2 SO 4 In the middle, a rare earth high-entropy alloy sample is taken as a working electrode, a Pt sheet is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode, constant potential passivation is carried out for 2 hours under the potential of 0.1V, and a layer of oxide film with the thickness of 220 mu m is formed on the surface.
Example 6
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Y 0.5 (ii) a The preparation method is the same as in example 1.
Example 7
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is the same as that of the alloy in embodiment 1;
the preparation process was carried out under the same conditions as in example 1 except that the first soaking temperature at 1500 ℃ in step (2).
Example 8
The embodiment provides an acid corrosion resistant rare earth high-entropy alloy and a preparation method thereof, wherein the chemical formula of the rare earth high-entropy alloy is the same as that of embodiment 1;
the preparation process was carried out under the same conditions as in example 1 except that the first keeping temperature at 450 ℃ in step (2).
Comparative example 1
The comparative example provides an acid corrosion resistant high-entropy alloy and a preparation method thereof, and the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 ；
The preparation method was the same as example 1 except that step (3) was not performed.
Comparative example 2
The comparative example provides an acid corrosion resistant high-entropy alloy and a preparation method thereof, and the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 La 0.01 (ii) a The preparation method is the same as in example 1.
Comparative example 3
The comparative example provides an acid corrosion resistant high-entropy alloy and a preparation method thereof, and the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 Pr 0.01 (ii) a The preparation method is the same as in example 1.
Comparative example 4
The comparative example provides an acid corrosion resistant high-entropy alloy and a preparation method thereof, and the chemical formula of the rare earth high-entropy alloy is FeCr 0.7 NiCu 0.5 Ti 0.5 (ii) a The preparation method is the same as in example 1.
Comparative example 5
The present comparative example provides an acid corrosion resistant rare earth high-entropy alloy having the same chemical formula as in example 1 and a method for preparing the same;
the preparation method was carried out under the same conditions as in example 1 except that the step (2) was not carried out.
Comparative example 6
The present comparative example provides an acid corrosion resistant rare earth high-entropy alloy having the same chemical formula as in example 1;
the preparation method was carried out under the same conditions as in example 1 except that the step (3) was not carried out.
The high-entropy alloys prepared in the above examples 1 to 5 and comparative examples 1 to 3 were subjected to an X-ray diffraction (XRD) test and a Scanning Electron Microscope (SEM) test, and the results are shown in fig. 1 and 2, respectively;
XRD test: the range of the scanning angle 2 theta is 20-100 degrees, and the scanning speed is 1 degree/min;
and (4) SEM test: using aqua regia to corrode the surface of the sample, and using a Zeiss microscope to observe the structure of the corroded sample;
the high-entropy alloys prepared in the above examples and comparative examples were subjected to a polarization curve test in a range of-0.6 to 1.5V, and the results are shown in Table 1, with examples 1 to 5 and comparative examples 1 to 3 being at 0.5mol/L H 2 SO 4 The polarization curve in (1) is shown in FIG. 3; the corrosion resistance test is to test a polarization curve after constant potential passivation in a 0.5mol/L sulfuric acid solution, and the standard is that the passivation current density is less than 1 multiplied by 10 -3 A/cm 2 。
TABLE 1
From table 1, the following points can be derived:
(1) The rare earth high-entropy alloy and the preparation method thereof have good acid corrosion resistance, and the content of the rare earth high-entropy alloy is 0.5mol/L H 2 SO 4 In the passivation current density of less than 1 x 10 -3 A/cm 2 ；
(2) It is known from the combination of the examples 1 and 6 that when the addition amount of the rare earth element is too large, the acid corrosion resistance of the rare earth high-entropy alloy is reduced due to too many alloy defects;
(3) It can be seen from the combination of the embodiment 1 and the embodiments 7 to 8 that when the annealing temperature is too high, the acid corrosion resistance of the rare earth high-entropy alloy is reduced due to the change of the internal structure of the alloy; when the annealing heat preservation temperature is too low, the acid corrosion resistance of the rare earth high-entropy alloy is not obviously changed because the alloy structure is not changed, but the cost is increased;
(4) By combining the embodiment 1 and the comparative examples 1 and 4, it can be known that when the high-entropy alloy is not doped with the rare earth elements, the generation of an oxidation film is not compact enough due to insufficient oxygen affinity of the alloy elements, and the acid corrosion resistance of the high-entropy alloy is reduced; when the high-entropy alloy is not passivated, the acid corrosion resistance of the high-entropy alloy is reduced because a compact passivation film with corresponding thickness is not generated;
(5) By combining the embodiment 1 and the comparative examples 2-3, the performance of the rare earth elements La and Pr is inferior to that of Sm, gd, Y and Ho, and the prepared rare earth high-entropy alloy has poor acid corrosion resistance;
(6) By combining the example 1 and the comparative examples 5 to 6, it can be seen that when the annealing treatment is not carried out, the internal structure of the alloy is more compact due to the failure of refinement and gold grain, so that the acid corrosion resistance of the rare earth high-entropy alloy is reduced; when constant potential passivation treatment is not carried out, the acid corrosion resistance of the high-entropy alloy is reduced because a dense passivation film with corresponding thickness is not generated.
The applicant states that the present invention is described by the above embodiments to explain the detailed structural features of the present invention, but the present invention is not limited to the above detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A kind ofThe acid corrosion resistant rare earth high-entropy alloy is characterized in that the chemical formula of the rare earth high-entropy alloy is FeCr a NiCu 0.5 Ti 0.5 RE x Wherein RE comprises any one or combination of at least two of Sm, gd, Y or Ho;
the molar ratio of Cr in the rare earth high-entropy alloy is more than or equal to 0.3 and less than or equal to 1.2;
the molar ratio of RE in the rare earth high-entropy alloy is more than or equal to 0.01 and less than or equal to 0.3.
2. A rare earth high entropy alloy according to claim 1, wherein the structure of the rare earth high entropy alloy is FCC phase, BCC phase and intermetallic compound;
preferably, the intermetallic compound precipitates out of the surface of the FCC phase.
3. The rare earth high-entropy alloy according to claim 1 or 2, wherein the rare earth high-entropy alloy is at or below 1mol/L H 2 SO 4 In the passivation current density of less than 1 x 10 -3 A/cm 2 。
4. A method for producing a rare earth high entropy alloy as claimed in any one of claims 1 to 3, wherein the method comprises: and sequentially carrying out vacuum melting, annealing and constant potential passivation on the alloy raw materials according to the molar ratio to obtain the rare earth high-entropy alloy.
5. The method of manufacturing according to claim 4, wherein the vacuum melting is: firstly melting Ti blocks, and then melting other alloy blocks to obtain a button ingot alloy;
preferably, the vacuum degree of the vacuum melting is less than 7 x 10 -3 MPa；
Preferably, the number of times of vacuum melting is more than or equal to 4 times, and preferably 4 to 6 times.
6. The production method according to claim 4 or 5, characterized in that the annealing is performed under a protective atmosphere;
preferably, the protective atmosphere comprises argon;
preferably, the annealing includes a first heat-retention, a first cooling, and a second cooling performed in this order.
7. The method according to claim 6, wherein the temperature of the first incubation is 500-1300 ℃;
preferably, the first heat preservation time is 6-24h;
preferably, the first cooling is furnace cooling;
preferably, the end temperature of the first cooling is 380 to 450 ℃;
preferably, the second cooling is air cooling.
8. The method of any one of claims 4-7, wherein the potentiostatic passivation comprises: preparing an alloy sample into an electrode by adopting resin, and then carrying out constant potential passivation in a three-electrode system to form an oxide film on the surface of the alloy sample;
preferably, before the constant potential passivation, the annealed button ingot alloy is sequentially polished and subjected to wire cutting to obtain an alloy sample.
9. The method of manufacturing according to claim 8, wherein the resin comprises an epoxy resin;
preferably, the potential of the potentiostatic passivation is from 0.1 to 1.0V;
preferably, the constant potential passivation time is more than or equal to 0.5h, and preferably 0.5-5h;
preferably, the electrolyte of the three-electrode system is H with the concentration less than or equal to 1mol/L 2 SO 4 ；
Preferably, the thickness of the oxide film is 1.0 to 300 μm.
10. The method for preparing a composite material according to any one of claims 4 to 9, comprising the steps of:
(1) Vacuum melting is carried out on the alloy raw materials according to the molar ratio, a Ti block is melted firstly, and then other alloys are melted to prepare a button ingot alloy;
the vacuum degree of the vacuum melting is less than 7 multiplied by 10 -3 MPa, the smelting times are more than or equal to 4;
(2) Annealing the button ingot alloy in the step (1) in a protective atmosphere;
the annealing comprises the steps of sequentially keeping the temperature at 500-1300 ℃ for 6-24h, then cooling to 450-380 ℃ along with the furnace, and finally taking out and air cooling;
(3) Sequentially polishing and linearly cutting the annealed button ingot alloy obtained in the step (2) to obtain an alloy sample, then preparing the alloy sample into an electrode by adopting epoxy resin, and then adopting a three-electrode system to obtain H with the concentration less than or equal to 1mol/L 2 SO 4 The constant potential passivation is carried out for more than or equal to 0.5h under the potential of 0.1-1.0V, and an oxide film with the thickness of 1.0-300 mu m is formed on the surface.
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