阅读说明：本技术 一种耐熔融锌腐蚀的复合材料及其制备方法 (Composite material resistant to corrosion of molten zinc and preparation method thereof ) 是由 尹冰冰 谢小龙 尹付成 王鑫铭 欧阳雪枚 胡静娴 于 2021-01-14 设计创作，主要内容包括：本发明实施例公开了一种耐熔融锌腐蚀的复合材料及其制备方法。本发明提供的复合材料的化学组成为FeB-Mo-AlFeNiCoCr,其显微硬度位于1405.2HV-(0.2)～1612.5HV-(0.2)范围内。所述复合材料的制备方法包括AlFeNiCoCr高熵合金的制备,FeB-Mo-AlFeNiCoCr复合粉末的制备和复合材料的制备等步骤。本发明实施例采用AlFeNiCoCr高熵合金和Mo作为粘结相,采用FeB作为硬质相,改善了传统金属陶瓷材料以Co、Ni等单质或合金作为粘结相因而容易被熔融锌腐蚀的情况,因而提高了材料的耐熔融锌腐蚀性能。另外所述复合材料的原材料成本低,所述复合材料的制备方法操作简便,所用设备平常可见,在锌工业中具有较高的应用价值。(The embodiment of the invention discloses a composite material resisting molten zinc corrosion and a preparation method thereof. The chemical composition of the composite material provided by the invention is FeB-Mo-AlFeNiCoCr, and the microhardness of the composite material is 1405.2HV 0.2 ～1612.5HV 0.2 Within the range. The preparation method of the composite material comprises the steps of preparing the AlFeNiCoCr high-entropy alloy, preparing FeB-Mo-AlFeNiCoCr composite powder, preparing the composite material and the like. According to the embodiment of the invention, the AlFeNiCoCr high-entropy alloy and Mo are used as the binder phase, and the FeB is used as the hard phase, so that the condition that the traditional metal ceramic material is easily corroded by molten zinc due to the fact that Co, Ni and other simple substances or alloys are used as the binder phase is improved, and the corrosion resistance of the material to molten zinc is improvedAnd (4) performance. In addition, the raw material cost of the composite material is low, the preparation method of the composite material is simple and convenient to operate, and the used equipment is common and visible, so that the composite material has high application value in the zinc industry.)

1. A preparation method of a composite material resisting molten zinc corrosion is characterized by comprising the following steps:

(X1) carrying out mechanical alloying on Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages as raw material powder to finally obtain powder after mechanical alloying;

(X2) subjecting the mechanically alloyed powder obtained in the step (X1) to primary vacuum drying to obtain a primary vacuum dried powder;

(X3) putting the powder subjected to the first vacuum drying in the step (X2) into a vacuum sintering furnace for first vacuum sintering, first grinding and first screening to obtain AlFeNiCoCr high-entropy alloy powder;

(X4) carrying out ball milling and mixing on 12 mass percent of AlFeNiCoCr high-entropy alloy powder, 5-15 mass percent of Mo powder and 73-83 mass percent of FeB powder to obtain powder after ball milling and mixing;

(X5) performing a second vacuum drying of the ball-milled mixed powder obtained in the step (X4) to obtain a second vacuum dried powder;

(X6) putting the powder subjected to the second vacuum drying in the step (X5) into the vacuum sintering furnace for second vacuum sintering, second grinding and second screening to obtain a composite powder;

(X7) performing spark plasma sintering on the composite powder obtained in the step (X6) to obtain the molten zinc corrosion resistant composite material.

2. The method for preparing a molten zinc corrosion resistant composite material according to claim 1, wherein the step (X1) specifically comprises:

polyethylene glycol is also added to the raw material powder in an amount of 1 wt.% based on the total mass of the raw material powder before the mechanical alloying is performed, so that the raw material powder and the polyethylene glycol are subjected to the mechanical alloying, and the mechanically alloyed powder is obtained.

3. The method for preparing the molten zinc corrosion resistant composite material according to claim 1, wherein the mechanical alloying time in the step (X1) is 50-60 h, the rotating speed is 300-350 r/min, and the ball-to-feed ratio is 8: 1-12: 1.

4. the method of preparing a molten zinc corrosion resistant composite material according to claim 1, wherein the conditions of the first vacuum drying in the step (X2) and the second vacuum drying in the step (X5) are the same, including: the temperature is 80-110 ℃, the vacuum degree is-0.1 MPa, and the time is 8-24 h.

5. The method of preparing a molten zinc corrosion resistant composite material according to claim 1, wherein the first vacuum sintering in the step (X3) and the second vacuum sintering in the step (X6) are performed by the same process comprising: vacuumizing the vacuum sintering furnace to 1 × 10^-8And (3) heating the mixture to 100 ℃ from room temperature at the speed of 1-3 ℃/min, heating the mixture to 360-430 ℃ from 100 ℃ at the speed of 3-5 ℃/min, preserving the heat at 360-430 ℃ for 70-100 min, heating the mixture to 950-1050 ℃ from 360-430 ℃ at the speed of 8-10 ℃/min, preserving the heat at 950-1050 ℃ for 120-180 min, and finally cooling the mixture to room temperature along with a furnace.

6. The method for preparing the molten zinc corrosion-resistant composite material according to claim 1, wherein the ball milling and mixing in the step (X4) are carried out for 1-3 h at a rotation speed of 150-250 r/min and a ball-to-material ratio of 2: 1-5: 1.

7. the method of preparing a molten zinc corrosion resistant composite material according to claim 1, wherein the pressure of the spark plasma sintering in the step (X7) is 50 to 90 MPa; the temperature rise procedure of the spark plasma sintering is as follows: heating from room temperature to 850-1100 ℃ at a heating rate of 160-210 ℃/min; then heating from 850-1100 ℃ to 1200-1500 ℃ at a heating rate of 25-55 ℃/min, and preserving heat for 4-10 min; and finally, cooling to room temperature along with the furnace.

8. The composite material resistant to molten zinc corrosion is characterized by comprising the following components in percentage by weight: 73-83% of FeB powder, 5-15% of Mo powder and 12% of AlFeNiCoCr high-entropy alloy powder; wherein the microhardness of the composite material is 1405.2HV_0.2～1612.5HV_0.2Within the range.

9. The molten zinc corrosion resistant composite material of claim 8, wherein the AlFeNiCoCr high entropy alloy powder is composed of the following components in mass percent: 1.96-2.9 percent of Al powder, 24.6-48.73 percent of Fe powder, 17.11-25.35 percent of Ni powder, 17.11-25.35 percent of Co powder and 15.09-22.34 percent of Cr powder.

10. The molten zinc corrosion resistant composite material of claim 9, wherein the AlFeNiCoCr high entropy alloy powder consists of the following components in mass percent: 2.9 percent of Al powder, 24.06 percent of Fe powder, 25.35 percent of Ni powder, 25.35 percent of Co powder and 22.34 percent of Cr powder.

Technical Field

The invention relates to the technical field of metal corrosion and protection, in particular to a composite material resistant to molten zinc corrosion and a preparation method thereof.

Background

Hot dip galvanization is one of the most economical and effective methods for protecting metallic materials such as steel from atmospheric corrosion. Hot-dip galvanized products are widely used for plates, pipes, wires, belts, and hardware electric parts because of their excellent corrosion resistance, formability, and decorativeness. However, molten zinc is very corrosive to almost all single metals and most alloys. The corrosion of metal melts is always a worldwide problem which puzzles the galvanizing industry. Particularly, the equipment or parts immersed in the molten metal are strongly corroded by the molten metal, so that the equipment is frequently replaced and the production efficiency is reduced. This not only brings huge economic loss, but also causes waste of resources. At present, the materials resistant to corrosion of molten zinc mainly comprise cobalt-based superalloy materials, ceramic materials, metal ceramic materials and the like. The cobalt-based superalloy material is expensive, general in molten zinc corrosion resistance, and large in brittleness of ceramic materials, and is easy to fail due to formation and propagation of cracks. The metal ceramic combines good toughness of metal and excellent corrosion resistance of ceramic, and has better molten zinc corrosion resistance compared with other materials. However, the metallic binder phase tends to be the primary cause of failure of the cermet in molten zinc.

Disclosure of Invention

Therefore, the embodiment of the invention provides the composite material resisting the corrosion of molten zinc and the preparation method thereof, FeB is used as a hard phase, and the composite material has good corrosion resistance; mo and AlFeNiCoCr high-entropy alloy are used as a binding phase, the AlFeNiCoCr high-entropy alloy improves the brittleness of boride, the wettability between Mo and Zn is poor, and eutectic reaction does not occur with Zn at 450 ℃, so that the problem of poor molten zinc corrosion resistance of the binding phase in the traditional metal ceramic material is solved, and the molten zinc corrosion resistance of the material is improved.

Specifically, in one aspect, a method for preparing a molten zinc corrosion resistant composite material provided by an embodiment of the present invention includes the steps of:

(X1) carrying out mechanical alloying on Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages as raw material powder to finally obtain powder after mechanical alloying;

(X2) subjecting the mechanically alloyed powder obtained in the step (X1) to primary vacuum drying to obtain a primary vacuum dried powder;

(X3) putting the powder subjected to the first vacuum drying in the step (X2) into a vacuum sintering furnace for first vacuum sintering, first grinding and first screening to obtain AlFeNiCoCr high-entropy alloy powder;

(X4) carrying out ball milling and mixing on 12 mass percent of AlFeNiCoCr high-entropy alloy powder, 5-15 mass percent of Mo powder and 73-83 mass percent of FeB powder to obtain powder after ball milling and mixing;

(X5) performing a second vacuum drying of the ball-milled mixed powder obtained in the step (X4) to obtain a second vacuum dried powder;

(X6) putting the powder subjected to the second vacuum drying in the step (X5) into the vacuum sintering furnace for second vacuum sintering, second grinding and second screening to obtain a composite powder;

(X7) performing spark plasma sintering on the composite powder obtained in the step (X6) to obtain the molten zinc corrosion resistant composite material.

In an embodiment of the present invention, the step (X1) specifically includes:

polyethylene glycol of 1 wt.% of the total mass of the raw material powder is also added before the mechanical alloying is carried out, so that the raw material powder and the polyethylene glycol are subjected to the mechanical alloying, and the powder after the mechanical alloying is obtained.

In one embodiment of the present invention, the mechanical alloying time in the step (X1) is 50 to 60 hours, the rotation speed is 300 to 350r/min, and the ball-to-material ratio is 8: 1-12: 1.

in one embodiment of the present invention, the conditions of the first vacuum drying in the step (X2) and the second vacuum drying in the step (X5) are the same, including: the temperature is 80-110 ℃, the vacuum degree is-0.1 MPa, and the time is 8-24 h.

In one embodiment of the present invention, the first vacuum sintering in the step (X3) and the second vacuum sintering in the step (X6) are the same in process, including: vacuumizing the vacuum sintering furnace to 1 × 10^-8And (3) heating the mixture to 100 ℃ from room temperature at the speed of 1-3 ℃/min, heating the mixture to 360-430 ℃ from 100 ℃ at the speed of 3-5 ℃/min, preserving the heat at 360-430 ℃ for 70-100 min, heating the mixture to 950-1050 ℃ from 360-430 ℃ at the speed of 8-10 ℃/min, preserving the heat at 950-1050 ℃ for 120-180 min, and finally cooling the mixture to room temperature along with a furnace.

In one embodiment of the present invention, the ball milling and mixing time in the step (X4) is 1 to 3 hours, the rotation speed is 150 to 250r/min, and the ball-to-material ratio is 2: 1-5: 1.

in one embodiment of the present invention, the pressure of the spark plasma sintering in the step (X7) is 50 to 90 MPa; the temperature rise procedure of the spark plasma sintering is as follows: heating from room temperature to 850-1100 ℃ at a heating rate of 160-210 ℃/min; then heating from 850-1100 ℃ to 1200-1500 ℃ at a heating rate of 25-55 ℃/min, and preserving heat for 4-10 min; and finally, cooling to room temperature along with the furnace.

On the other hand, the embodiment of the invention provides a molten zinc corrosion resistant composite material, which comprises the following components in percentage: 73-83% of FeB powder, 5-15% of Mo powder and 12% of AlFeNiCoCr high-entropy alloy powder; wherein the microhardness of the composite material is 1405.2HV_0.2～1612.5HV_0.2Within the range.

In one embodiment of the invention, the AlFeNiCoCr high-entropy alloy powder consists of the following components in percentage by mass: 1.96-2.9 percent of Al powder, 24.6-48.73 percent of Fe powder, 17.11-25.35 percent of Ni powder, 17.11-25.35 percent of Co powder and 15.09-22.34 percent of Cr powder.

In one embodiment of the invention, the AlFeNiCoCr high-entropy alloy powder consists of the following components in percentage by mass: 2.9 percent of Al powder, 24.06 percent of Fe powder, 25.35 percent of Ni powder, 25.35 percent of Co powder and 22.34 percent of Cr powder.

The above technical solution may have one or more of the following advantages: (1) the composite material resistant to molten zinc corrosion provided by the embodiment of the invention adopts FeB as a hard phase, adopts AlFeNiCoCr high-entropy alloy and Mo as a binder phase, and elements in the AlFeNiCoCr high-entropy alloy are dissolved in the FeB in a solid manner and form Fe in a vacuum sintering process₂B and Mo has excellent molten zinc corrosion resistance and does not perform eutectic reaction with Zn at 450 ℃, thereby making up the defect of poor molten zinc corrosion resistance of the binding phase. (2) The preparation method of the molten zinc corrosion resistant composite material provided by the embodiment of the invention is simple and convenient to operate, the used equipment is common, the raw materials are convenient to obtain, and the production and application are facilitated.

Drawings

FIG. 1 is a scanning electron microscope image of AlFeNiCoCr high-entropy alloy powder after vacuum sintering, wherein a, b and c are Al respectively_0.25FeNiCoCr、Al_0.25Fe₂NiCoCr、Al_0.25Fe₃Scanning electron microscope images of NiCoCr high-entropy alloy powder after vacuum sintering;

FIG. 2 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite powder after ball milling and mixing, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25Scanning electron microscope images of the FeNiCoCr composite powder after ball milling and mixing;

FIG. 3 is an XRD pattern of FeB-Mo-12 wt.% AlFeNiCoCr composite powder after ball milling mixing;

FIG. 4 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite powder after vacuum sintering, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25After vacuum sintering of FeNiCoCr composite powderScanning an electron microscope image;

FIG. 5 is an XRD pattern of a FeB-Mo-AlFeNiCoCr composite powder after vacuum sintering;

FIG. 6 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite material, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25Scanning electron microscope images of the FeNiCoCr composite material;

FIG. 7 is FeB-10 wt.% Mo-12 wt.% Al_0.25Scanning electron microscope images of the FeNiCoCr composite material after being corroded in molten zinc at 450 ℃ for 30 days;

FIG. 8 is FeB-15 wt.% Mo-12 wt.% Al_0.25Scanning electron microscope images of the FeNiCoCr composite material after being corroded in molten zinc at 450 ℃ for 5 days;

fig. 9 is a schematic flow chart of a method for preparing a molten zinc corrosion resistant composite material according to an embodiment of the present invention.

Detailed Description

In order to facilitate understanding of the present invention, the present invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the present invention is not limited to the following embodiments.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Referring to fig. 9, it is a flow chart of a method for preparing a molten zinc corrosion resistant composite material according to an embodiment of the present invention. Specifically, an embodiment of the present invention provides a method for preparing a molten zinc corrosion resistant composite material:

(S1) adding Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages as raw material powder into a ball mill for mechanical alloying. Specifically, the ratio of 8: 1-12: adding grinding balls according to the ball-to-material ratio (mass ratio) of 1, pouring 1 wt.% of polyethylene glycol based on the total mass of the raw material powder to improve the formability of the powder in vacuum sintering, and performing ball milling at the rotating speed of 300-350 r/min for 50-60 h to obtain the uniformly mixed powder after mechanical alloying. The preset mass percentage is, for example: 1.96-2.9 percent of Al powder, 24.6-48.73 percent of Fe powder, 17.11-25.35 percent of Ni powder, 17.11-25.35 percent of Co powder and 15.09-22.34 percent of Cr powder. Of course, the preset mass percentage may be other proportions, and the invention is not limited thereto.

(S2) performing first vacuum drying on the mechanically alloyed powder to obtain a first vacuum dried powder. Specifically, the first vacuum drying includes drying the powder obtained after the mechanical alloying in the step (S1) for 8-24 hours at 80-110 ℃ and under a vacuum environment of-0.1 MPa to obtain the powder after the first vacuum drying.

(S3) putting the powder obtained in the step (S2) after the first vacuum drying into a vacuum sintering furnace for first vacuum sintering, first grinding and first screening to obtain the AlFeNiCoCr high-entropy alloy powder. Wherein, the first vacuum sintering specifically comprises: vacuumizing the vacuum sintering furnace to 1 × 10^-8And (3) heating the mixture to 100 ℃ from room temperature at the speed of 1-3 ℃/min, heating the mixture to 360-430 ℃ from 100 ℃ at the speed of 3-5 ℃/min, preserving the heat at 360-430 ℃ for 70-100 min, heating the mixture to 950-1050 ℃ from 360-430 ℃ at the speed of 8-10 ℃/min, preserving the heat at 950-1050 ℃ for 120-180 min, and finally cooling the mixture to room temperature along with a furnace. And then, taking out the sintered blank, grinding the blank for the first time by using a mortar, and then screening for the first time by using a stainless steel screen of 60-400 meshes to obtain the AlFeNiCoCr high-entropy alloy powder.

(S4) carrying out ball milling and mixing on 12 mass percent of AlFeNiCoCr high-entropy alloy powder, 5-15 mass percent of Mo powder and 73-83 mass percent of FeB powder, wherein the ball material ratio is 2: 1-5: 1 (mass ratio) and adding polyethylene glycol accounting for 1 wt.% of the total mass of the raw material powder before ball milling to improve the formability of the powder in vacuum sintering, and ball milling at a rotating speed of 150-250 r/min for 1-3 h to obtain the ball-milled and mixed powder.

(S5) performing a second vacuum drying on the ball-milled and mixed powder obtained in the step (S4) to obtain a second vacuum dried powder, wherein the second vacuum drying process is the same as the first vacuum drying process in the step (S2).

(S6) putting the powder subjected to the second vacuum drying in the step (S5) into the vacuum sintering furnace for second vacuum sintering, second grinding and second screening to obtain FeB-Mo-AlFeNiCoCr composite powder. Wherein the second vacuum sintering process is the same as the first vacuum sintering process in the step (S3).

(S7) performing discharge plasma sintering on the FeB-Mo-AlFeNiCoCr composite powder obtained in the step (S6) to obtain the FeB-Mo-AlFeNiCoCr composite material. Specifically, the pressure of the spark plasma sintering is 50-90 MPa; the temperature rise procedure of the spark plasma sintering is as follows: heating from room temperature to 850-1100 ℃ at a heating rate of 160-210 ℃/min; then heating from 850-1100 ℃ to 1200-1500 ℃ at a heating rate of 25-55 ℃/min, and preserving heat for 4-10 min; and finally, cooling to room temperature along with the furnace.

According to the embodiment of the invention, through the steps, the finally obtained FeB-Mo-AlFeNiCoCr composite material is a block, strip and other non-powder sample, and can be directly used for preparing parts, equipment and the like resistant to molten zinc corrosion, such as a sink roll used in a hot-dip galvanizing process, a clamp used for clamping a plated part and the like.

In order to facilitate a better understanding of the examples of the invention, the method of making the molten zinc corrosion resistant composite of the examples of the invention is described in detail below by six tests.

(1) Preparing the AlFeNiCoCr high-entropy alloy:

[ TEST I ]

(X1) according to the mass percent of each element: al powder 2.9%, Fe powder 24.06%, Ni powder 25.35%, Co powder 25.35%, and Cr powder 22.34%, each 50.000g of Al powder 1.450g, Fe powder 12.030g, Ni powder 12.675g, Co powder 12.675g, and Cr powder 11.170g, each having a purity of 99.9% and an average particle diameter of 2 μm, were weighed by an electronic balance, and added to a ball mill pot of a ball mill, and polyethylene glycol was added thereto in an amount of 1% by mass of the raw material powder, i.e., 50 × 1% ═ 0.5g of polyethylene glycol, and the mixture was mixed in 10: 1, adding a stainless steel grinding ball according to the ball-to-material ratio (mass ratio), pouring 45ml of absolute ethyl alcohol, and carrying out ball milling for 50h at the rotating speed of 300r/min to obtain the powder after mechanical alloying.

(X2) drying the powder obtained by the mechanical alloying in the step (X1) in vacuum for 24 hours at 100 ℃ and under the vacuum condition of-0.1 MPa to obtain the powder after vacuum drying.

(X3) putting the vacuum-dried powder obtained in step (X2) into a vacuum sintering furnace for vacuum sintering, grinding and sieving. Wherein, the vacuum sintering specifically comprises: vacuumizing the vacuum sintering furnace to 1 × 10^-8Raising the temperature from room temperature to 100 ℃ at the speed of 2 ℃/min, raising the temperature from 100 ℃ to 960 ℃ at the speed of 5 ℃/min, preserving the heat at 960 ℃ for 16min, and finally cooling to the room temperature along with the furnace; then taking out the sintered blank, grinding the blank by using a mortar, and screening by using a 60-mesh stainless steel sieve to obtain Al_0.25The morphology of the FeNiCoCr high-entropy alloy powder is shown in a figure 1 (a).

[ TEST II ]

The preparation method in [ test two ] is mostly the same as that in [ test one ], except that:

1) step (X1): according to the mass percent of each element: 2.34% of Al powder, 38.79% of Fe powder, 20.43% of Ni powder, 20.43% of Co powder and 18.01% of Cr powder. For example, 60.000g of Al powder 1.404g, Fe powder 23.274g, Ni powder 12.258g, Co powder 12.258g and Cr powder 10.806g each having a purity of 99.9% and an average particle diameter of 2 μm were weighed out on an electronic balance and charged into a ball mill pot of a ball mill, and 0.6000g of polyethylene glycol was further added thereto so as to give a powder of 10: 1, adding a stainless steel grinding ball, pouring 55ml of absolute ethyl alcohol, and carrying out ball milling for 55h at the rotating speed of 300r/min to obtain powder after mechanical alloying.

2) Step (X3): to obtain Al_0.25Fe₂The morphology of the NiCoCr high-entropy alloy powder is shown in a figure 1 (b).

[ TEST III ]

The preparation method of [ test three ] is mostly the same as that of [ test one ], except that:

1) step (X1): according to the mass percent of each element: al powder 1.96%, Fe powder 48.73%, Ni powder 17.11%, Co powder 17.11%, and Cr powder 15.09%, Al powder 1.176g, Fe powder 29.238g, Ni powder 10.266g, Co powder 10.266g, and Cr powder 9.054g, each having a purity of 99.9% and an average particle diameter of 2 μm, were weighed by an electronic balance, for example, to 60.000g in total, and 0.600g of polyethylene glycol was added thereto so as to prepare a mixture of 11: 1, adding a stainless steel grinding ball according to the ball-to-material ratio (mass ratio), pouring 60ml of absolute ethyl alcohol, and carrying out ball milling for 60 hours at the rotating speed of 320r/min to obtain powder after mechanical alloying.

2) Step (X3): to obtain Al_0.25Fe₃The morphology of the NiCoCr high-entropy alloy powder is shown in figure 1 (c).

(II) preparing a FeB-Mo-AlFeNiCoCr composite material:

[ TEST FOUR ]

(Y1) according to mass percent: al (Al)_0.2512% of FeNiCoCr high-entropy alloy powder, 5% of Mo powder and 83% of Fe powder, for example, Al powder is weighed by an electronic balance_0.257.200g of FeNiCoCr high-entropy alloy powder, 3.000g of Mo powder and 49.800g of FeB powder, which account for 60.000g, are put into a ball milling tank of a ball mill, and 0.600g of polyethylene glycol is additionally added, so that the weight ratio of the mixture is 3: 1, filling stainless steel grinding balls according to the ball-to-material ratio (mass ratio) of 1, pouring 50ml of absolute ethyl alcohol, and performing ball milling for 2 hours at the rotating speed of 200r/min to obtain powder after ball milling and mixing; wherein the aforementioned Al_0.25FeNiCoCr high entropy alloy powder, for example, Al obtained in [ test one ] step (X3)_0.25FeNiCoCr high-entropy alloy powder.

(Y2) the powder obtained by the ball-milling and mixing in the step (Y1) was dried in vacuum at 90 ℃ under a vacuum of-0.1 MPa for 24 hours.

(Y3) putting the powder obtained after the vacuum drying in the step (Y2) into a vacuum sintering furnace for vacuum sintering, grinding and screening to obtain FeB-5 wt.% Mo-12 wt.% Al_0.25The morphology of the FeNiCoCr composite powder is shown in FIG. 4 (a). Wherein the vacuum sintering comprises: vacuumizing the vacuum sintering furnace to 1 × 10^-8MPa, raising the temperature from room temperature to 100 ℃ at the speed of 2 ℃/min, raising the temperature from 100 ℃ to 400 ℃ at the speed of 5 ℃/min, keeping the temperature at 400 ℃ for 90min, raising the temperature from 400 ℃ to 1000 ℃ at the speed of 8 ℃/min, and keeping the temperature at 1000 ℃ for 1And (5) 60min, and finally cooling to room temperature along with the furnace. Here, the grinding process in this step was the same as that in [ test one ], and a 400-mesh stainless steel sieve was used for the sieving.

(Y4) FeB-5 wt.% Mo-12 wt.% Al obtained in step (Y3)_0.25Performing discharge plasma sintering on the FeNiCoCr composite powder, wherein the pressure of the discharge plasma sintering is 60 MPa; the temperature rising procedure of the spark plasma sintering is as follows: heating from room temperature to 900 ℃ at a heating rate of 160 ℃/min; then heating from 900 ℃ to 1400 ℃ at a heating rate of 50 ℃/min, and preserving heat at 1400 ℃ for 6 min; finally, cooling to room temperature along with the furnace to obtain FeB-5 wt.% Mo-12 wt.% Al resistant to molten zinc corrosion_0.25The morphology of the FeNiCoCr composite material is shown in FIG. 6 (a).

[ TEST FIVE ]

The preparation method in [ test five ] is mostly the same as that of [ test four ], except that:

1) step (Y1): according to the mass percentage: al (Al)_0.2512% of FeNiCoCr high-entropy alloy powder, 10% of Mo powder and 78% of Fe powder, for example, Al powder is weighed by an electronic balance_0.257.200g of FeNiCoCr high-entropy alloy powder, 6.000g of Mo powder and 46.800g of FeB powder which are 60.000g in total are put into a ball milling tank of a ball mill for ball milling and powder mixing to obtain powder after ball milling and mixing;

2) step (Y3): FeB-10 wt.% Mo-12 wt.% Al is obtained_0.25The morphology of the FeNiCoCr composite powder is shown in FIG. 4 (b).

3) Step (Y4): FeB-10 wt.% Mo-12 wt.% Al is obtained_0.25The morphology of the FeNiCoCr composite material is shown in FIG. 6 (b).

[ TEST HEI ]

The preparation method in [ test six ] is mostly the same as that of [ test four ], except that:

1) step (Y1): according to the mass percentage: al (Al)_0.2512% of FeNiCoCr high-entropy alloy powder, 15% of Mo powder and 73% of Fe powder, for example, Al powder is weighed by an electronic balance_0.257.200g of FeNiCoCr high-entropy alloy powder, 9.000g of Mo powder and 43.800g of FeB powder which are 60.000g in total are put into a ball milling tank of a ball mill for ball milling and mixing to obtain the ball milled and mixed powderPowder;

2) step (Y3): to give FeB-15 wt.% Mo-12 wt.% Al_0.25The morphology of the FeNiCoCr composite powder is shown in FIG. 4 (c).

3) Step (Y4): to give FeB-15 wt.% Mo-12 wt.% Al_0.25The morphology of the FeNiCoCr composite material is shown in FIG. 6 (c).

To verify the FeB-Mo-Al obtained by the above-mentioned production methods_0.25The corrosion resistance of the FeNiCoCr composite material is tested by the invention. Firstly, placing samples in different graphite crucibles containing molten zinc, heating the graphite crucibles by using a shaft furnace, keeping the temperature of the molten zinc at 450 ℃, respectively corroding the samples for 5 days, 10 days, 20 days and 30 days, then taking out the samples, analyzing the texture of a corrosion interface between the composite material and the molten zinc by using a scanning electron microscope, and then measuring the element distribution condition of the samples after corrosion in the molten zinc by using an energy spectrometer.

FeB-Mo-Al obtained by different grouping tests_0.25Detecting and analyzing the morphology, phase and performance of the FeNiCoCr powder and the composite material:

1) FIG. 1 is a scanning electron microscope image of AlFeNiCoCr high-entropy alloy powder after vacuum sintering, wherein a, b and c are Al respectively_0.25FeNiCoCr、Al_0.25Fe₂NiCoCr、Al_0.25Fe₃Scanning electron microscope images of NiCoCr high-entropy alloy powder after vacuum sintering. As shown in fig. 1, as the content of Fe element increases, the particle size of the powder after sintering gradually becomes coarse. However, the use of fine powders to make the composite material results in a more dense composite material with more difficulty in the penetration of molten zinc into the interior of the material. As can be seen, Al is preferable_0.25FeNiCoCr high-entropy alloy powder is used for preparing the composite material.

2) FIG. 2 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite powder after ball milling and mixing, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25Scanning electron microscopy images of the FeNiCoCr composite powder after ball milling mixing. As shown in fig. 2As shown, the composite powder after ball milling was uniform and polygonal.

3) FIG. 3 is FeB-Mo-12 wt.% Al_0.25XRD pattern of FeNiCoCr composite powder after ball milling mixing. As shown in FIG. 3, the phase of the composite powder after ball milling consisted of FeB, Mo and FCC solid solution (Al)_0.25FeNiCoCr high-entropy alloy), and no phase change occurs in the ball milling process.

4) FIG. 4 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite powder after vacuum sintering, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25Scanning electron microscope images of the FeNiCoCr composite powder after vacuum sintering. As shown in fig. 4, the powders after vacuum sintering are uniform and have a close particle size.

5) FIG. 5 is an XRD pattern of a FeB-Mo-AlFeNiCoCr composite powder after vacuum sintering; as shown in FIG. 5, the phase of the composite powder after vacuum sintering is made of FeB and Fe₂B and Mo, part of FeB is converted into Fe in the vacuum sintering process₂B, solid solution of high-entropy alloy in binding phase to FeB and Fe₂B, and Mo in the binder phase does not react chemically to form a new phase. The invention creatively adopts AlFeNiCoCr high-entropy alloy and Mo as a binding phase, and the AlFeNiCoCr high-entropy alloy is dissolved in FeB and Fe in a solid manner₂B is used for improving the brittleness of the metal, Mo has excellent molten zinc corrosion resistance and does not have eutectic reaction with Zn at 450 ℃, so that the problem that the conventional metal ceramic or composite material is always ineffective in molten zinc due to a binding phase is solved, and an unexpected effect is achieved.

6) FIG. 6 is a scanning electron micrograph of a FeB-Mo-AlFeNiCoCr composite material, wherein a, b, and c are FeB-5 wt.% Mo-12 wt.% Al, respectively_0.25FeNiCoCr、FeB-10wt.％Mo-12wt.％Al_0.25FeNiCoCr、FeB-15wt.％Mo-12wt.％Al_0.25Scanning electron micrographs of the FeNiCoCr composite, wherein black represents pores.

7) FIG. 7 is FeB-10 wt.% Mo-12 wt.% Al_0.25Scanning of FeNiCoCr composite after 30 days of corrosion in molten zinc at 450 DEG CAnd (3) an electron microscope image, wherein a is the appearance of the corrosion interface, and b is the Zn element distribution of the corrosion interface. As shown in fig. 7(a), the following are provided in order from right to left: zinc layer, base member. After 30 days of corrosion in molten zinc at 450 ℃, the Zn element mainly diffuses into the composite without forming strong dissolution and corrosion on the composite, indicating that the composite has excellent molten zinc corrosion resistance, mainly due to the phase composition of the hard phase and the binder phase in the composite.

8) FIG. 8 is FeB-15 wt.% Mo-12 wt.% Al_0.25Scanning electron microscopy images of the FeNiCoCr composite after 5 days of corrosion in molten zinc at 450 ℃. As shown in fig. 8, the composite material was hardly corroded by the molten zinc after 5 days of corrosion in the molten zinc at 450 ℃, indicating that it exhibited excellent corrosion resistance in the molten zinc.

In addition, the invention also provides a method for preparing FeB-Mo-Al by using MH-5L micro Vickers hardness meter_0.25The samples of the FeNiCoCr composite material were subjected to microhardness testing. Wherein the load is 200g, the loading time is 15 seconds, each sample selects 6 different positions, and the microhardness of the obtained sample is 1405.2HV_0.2～1612.5HV_0.2Within the range.

The above technical solution may have one or more of the following advantages: (1) the composite material resistant to molten zinc corrosion provided by the embodiment of the invention adopts FeB as a hard phase, adopts AlFeNiCoCr high-entropy alloy and Mo as a binder phase, and elements in the AlFeNiCoCr high-entropy alloy are dissolved in the FeB in a solid manner and form Fe in a vacuum sintering process₂B and Mo has excellent molten zinc corrosion resistance and does not perform eutectic reaction with Zn at 450 ℃, thereby making up the defect of poor molten zinc corrosion resistance of the binding phase. (2) The preparation method of the molten zinc corrosion resistant composite material provided by the embodiment of the invention is simple and convenient to operate, the used equipment is common, the raw materials are convenient to obtain, and the production and application are facilitated.

Finally, it should be noted that: the embodiments are only for the purpose of facilitating understanding of the technical solutions of the present invention, and do not constitute a limitation to the scope of the present invention, and any simple modification, equivalent change and modification made to the above solutions without departing from the contents of the technical solutions of the present invention or the technical spirit of the present invention still fall within the scope of the present invention.