阅读说明：本技术 耐熔融铝腐蚀的二硼化锆基金属陶瓷复合材料制备方法 (Preparation method of fused aluminum corrosion resistant zirconium diboride-based cermet composite material ) 是由 尹付成 任可柱 谢小龙 易华清 高志栋 于 2020-12-25 设计创作，主要内容包括：本发明实施例公开了一种耐熔融铝腐蚀的二硼化锆基金属陶瓷复合材料的制备方法。该复合材料的制备方法包括：将Al粉、Fe粉、Ni粉、Co粉、Cr粉进行第一球磨工艺和第一真空干燥工艺处理得到AlFeNiCoCr高熵合金粉末；将质量百分比为70％-88％的ZrB-2粉末和质量百分比为12％-30％的AlFeNiCoCr高熵合金粉末进行第二球磨工艺和第二真空干燥工艺以及放电等离子烧结处理。本发明实施例以AlFeNiCoCr高熵合金作为粘结相,ZrB-2作为硬质相,利用高熵合金所具备的高熵效应,改善了传统金属陶瓷材料以Co、Ni等单质作为粘结相而出现容易被熔融铝腐蚀的情况,较好地提高了二硼化锆基金属陶瓷复合材料的熔融铝腐蚀性能和使用寿命,并且该复合材料制作方法简单,成本低廉,在工业应用中有良好的前景。(The embodiment of the invention discloses a preparation method of a zirconium diboride-based cermet composite material resistant to molten aluminum corrosion. The preparation method of the composite material comprises the following steps: carrying out first ball milling process and first vacuum drying process treatment on Al powder, Fe powder, Ni powder, Co powder and Cr powder to obtain AlFeNiCoCr high-entropy alloy powder; ZrB with the mass percent of 70-88 percent 2 And performing a second ball milling process, a second vacuum drying process and discharge plasma sintering treatment on the powder and 12-30 mass percent of AlFeNiCoCr high-entropy alloy powder. The embodiment of the invention uses AlFeNiCoCr with high contentEntropy alloy as a binder phase, ZrB 2 As a hard phase, the high entropy effect of the high entropy alloy is utilized, the condition that the traditional metal ceramic material is easily corroded by molten aluminum due to the fact that Co, Ni and other simple substances are used as binding phases is improved, the molten aluminum corrosion performance and the service life of the zirconium diboride-based metal ceramic composite material are well improved, and the composite material is simple in manufacturing method, low in cost and good in prospect in industrial application.)

1. A preparation method of a zirconium diboride-based cermet composite material resistant to molten aluminum corrosion is characterized by comprising the following steps:

mixing 10.7% by mass, 22.1% by mass, 23.3% by mass and 20.6% by mass of Al powder, Fe powder, Ni powder, Co powder and Cr powder, adding into a ball mill, and adding 50-100ml of absolute ethyl alcohol to perform first ball milling process treatment to obtain a first ball milled mixture, wherein the ball milling time is 50-80h, and the ball milling revolution is 200-300 r/min;

carrying out first vacuum drying process treatment on the mixture after the first ball milling to obtain AlFeNiCoCr high-entropy alloy powder, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa;

adding 70-88% by mass of zirconium diboride powder and 12-30% by mass of AlFeNiCoCr high-entropy alloy powder into a ball mill, and adding 50-100ml of absolute ethyl alcohol to perform second ball milling process treatment to obtain a second ball-milled mixture;

carrying out second vacuum drying process treatment on the second ball-milled mixture to obtain a second dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa;

and (3) performing discharge plasma sintering in the second dried mixture plasma sintering furnace, heating to 1300-1500 ℃ at the heating rate of 50 ℃/min, and keeping the temperature for 4-6min, wherein the pressure in the plasma sintering furnace is 30-50MPa, so as to obtain the zirconium diboride-based metal ceramic composite material.

2. A preparation method of a zirconium diboride-based cermet composite material resistant to molten aluminum corrosion is characterized by comprising the following steps:

putting Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages into a ball mill to perform a first ball milling process treatment to obtain a first ball milled mixture;

carrying out first vacuum drying process treatment on the mixture subjected to the first ball milling treatment to obtain AlFeNiCoCr high-entropy alloy powder;

performing second ball milling process treatment on 70-88% by mass of zirconium diboride powder and 12-30% by mass of AlFeNiCoCr high-entropy alloy powder to obtain a second ball-milled mixture;

carrying out secondary vacuum drying process treatment on the second ball-milled mixture to obtain a second dried mixture; and

and performing discharge plasma sintering treatment on the second dried mixture to obtain the zirconium diboride-based cermet composite material.

3. The method for preparing the zirconium diboride-based cermet composite material according to claim 1, wherein the predetermined mass percentages are 10.7% of Al powder, 22.1% of Fe powder, 23.3% of Ni powder, 23.3% of Co powder, and 20.6% of Cr powder.

4. The method for preparing the zirconium diboride-based cermet composite material according to claim 1, wherein the first ball milling process comprises the steps of putting the Al powder, the Fe powder, the Ni powder, the Co powder and the Cr powder into a planetary ball mill, and adding a ball-to-material ratio of 10: 1-20: 1, introducing absolute ethyl alcohol to perform wet ball milling to obtain the mixture after the first ball milling, wherein the ball milling time is 50-80h, and the ball milling revolution is 200-300 r/min.

5. The method of preparing a zirconium diboride-based cermet composite material according to claim 1 wherein the first vacuum drying process comprises: and putting the mixture subjected to the first ball milling into a vacuum drying oven for vacuum drying treatment to obtain the AlFeNiCoCr high-entropy alloy powder, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa.

6. The method of preparing a zirconium diboride-based cermet composite material according to claim 1 wherein the second ball milling process comprises: and (2) loading the zirconium diboride powder and the AlFeNiCoCr high-entropy alloy powder into a planetary ball mill, wherein the ball-to-material ratio is 10: 1 stainless steel ball with the diameter of 10mm, adding 50ml of absolute ethyl alcohol, and performing wet ball milling to obtain a second ball-milled mixture, wherein the ball milling time is 5-10h, and the ball milling revolution is 200-300 r/min.

7. The method of preparing a zirconium diboride-based cermet composite material according to claim 1 wherein the second vacuum drying process comprises: and putting the mixture subjected to the second ball milling into a vacuum drying oven for vacuum drying treatment to obtain a second dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa.

8. The method of preparing a zirconium diboride-based cermet composite material according to claim 1 wherein the plasma sintering process comprises: and putting the mixture subjected to the second drying into a plasma sintering furnace for spark plasma sintering, heating to 1300-1500 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 4-6min, wherein the pressure in the plasma sintering furnace is 30-50 MPa.

9. The method of preparing a zirconium diboride-based cermet composite material resistant to corrosion by molten aluminum according to any of claims 1-8 wherein the zirconium diboride-based cermet composite material has zirconium diboride as the hard phase and AlFeNiCoCr high entropy alloy as the binder phase.

10. The method of making a zirconium diboride-based cermet composite material resistant to corrosion by molten aluminum according to claim 9 wherein the zirconium diboride-based cermet composite material has an average corrosion rate of 0.89 x 10 in a molten aluminum bath at a temperature of 700 ℃^-3-1.17×10^-3mm/h。

Technical Field

The invention belongs to the technical field of preparation of metal ceramic materials, and particularly relates to a preparation method of a zirconium diboride-based metal ceramic composite material resistant to molten aluminum corrosion.

Background

Hot dip aluminizing is one of the most commonly used hot dip coating protection means in the fields of chemical industry, building, traffic, manufacturing, metallurgy, ships and the like at present. Compared with hot dip galvanizing, hot dip aluminizing has good corrosion resistance, high temperature oxidation resistance and long service life. However, the property of aluminum is relatively active, and molten aluminum liquid is one of metal liquids with the strongest corrosiveness, so that the hot dip aluminum plating technology has the defect that the molten aluminum melt has unavoidable defects, the molten aluminum melt has great corrosiveness to hot dip aluminum plating equipment, and equipment such as an aluminum liquid loading tank, a sink roll and the like in a hot dip aluminum plating production line can be permeated by the aluminum liquid to generate aluminum slag and pitting corrosion, so that the quality of a hot-plated aluminum layer is poor, the service life of the hot dip aluminum plating equipment is shortened, and the problem of molten aluminum corrosion resistance of hot dip aluminum plating equipment materials is solved, and the development of the aluminum industry is greatly influenced.

Therefore, the problem that the service life of hot dip aluminum plating equipment such as a sink roll and the like is improved by providing a material with good molten aluminum corrosion resistance is needed to be solved.

Disclosure of Invention

The invention mainly aims to provide a preparation method of a zirconium diboride-based metal ceramic composite material with resistance to molten aluminum corrosion, aiming at the defects and shortcomings in the prior art, the method is easy to implement, and the zirconium diboride-based metal ceramic composite material prepared by the method has excellent resistance to molten aluminum corrosion.

The technical solution of the invention is as follows:

a preparation method of a zirconium diboride-based cermet composite material resistant to molten aluminum corrosion comprises the following steps: mixing 10.7% by mass, 22.1% by mass, 23.3% by mass and 20.6% by mass of Al powder, Fe powder, Ni powder, Co powder and Cr powder, adding into a ball mill, and adding 50-100ml of absolute ethyl alcohol to perform first ball milling process treatment to obtain a first ball milled mixture, wherein the ball milling time is 50-80h, and the ball milling revolution is 200-300 r/min; carrying out first vacuum drying process treatment on the mixture after the first ball milling to obtain AlFeNiCoCr high-entropy alloy powder, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa; adding 70-88% by mass of zirconium diboride powder and 12-30% by mass of AlFeNiCoCr high-entropy alloy powder into a ball mill, and adding 50-100ml of absolute ethyl alcohol to perform second ball milling process treatment to obtain a second ball-milled mixture; carrying out second vacuum drying process treatment on the second ball-milled mixture to obtain a second dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa; and performing discharge plasma sintering in the second dried mixture plasma sintering furnace, heating to 1300-1500 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 4-6min, wherein the pressure in the plasma sintering furnace is 30-50MPa, so as to obtain the zirconium diboride-based metal ceramic composite material.

The embodiment of the invention provides a preparation method of a zirconium diboride-based metal ceramic composite material resistant to molten aluminum corrosion, which comprises the following steps: putting Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages into a ball mill to perform a first ball milling process treatment to obtain a first ball milled mixture; carrying out first vacuum drying process treatment on the mixture subjected to the first ball milling treatment to obtain AlFeNiCoCr high-entropy alloy powder; performing second ball milling process treatment on 70-88% by mass of zirconium diboride powder and 12-30% by mass of AlFeNiCoCr high-entropy alloy powder to obtain a second ball-milled mixture; carrying out second vacuum drying process treatment on the second ball-milled mixture to obtain a second dried mixture; and performing discharge plasma sintering treatment on the second dried mixture to obtain the zirconium diboride-based cermet composite material.

In the embodiment of the invention, the preset mass percentage is 10.7% of Al powder, 22.1% of Fe powder, 23.3% of Ni powder, 23.3% of Co powder and 20.6% of Cr powder.

In an embodiment of the present invention, the first ball milling process treatment includes loading the Al powder, the Fe powder, the Ni powder, the Co powder, and the Cr powder into a planetary ball mill, and adding a powder having a ball-to-material ratio of 10: 1-20: 1, introducing absolute ethyl alcohol to perform wet ball milling to obtain the mixture after the first ball milling, wherein the ball milling time is 50-80h, and the ball milling revolution is 200-300 r/min.

In an embodiment of the present invention, the first vacuum drying process comprises: and putting the mixture subjected to the first ball milling into a vacuum drying oven for vacuum drying treatment to obtain the AlFeNiCoCr high-entropy alloy powder, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa.

In an embodiment of the present invention, the second ball milling process comprises: and (2) loading the zirconium diboride powder and the AlFeNiCoCr high-entropy alloy powder into a planetary ball mill, wherein the ball-to-material ratio is 10: 1 stainless steel ball with the diameter of 10mm, adding 50ml of absolute ethyl alcohol, and performing wet ball milling to obtain a second ball-milled mixture, wherein the ball milling time is 5-10h, and the ball milling revolution is 200-300 r/min.

In an embodiment of the present invention, the second vacuum drying process comprises: and putting the mixture subjected to the second ball milling into a vacuum drying oven for vacuum drying treatment to obtain a mixture subjected to second drying, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.1 MPa.

In an embodiment of the present invention, the plasma sintering process comprises: and putting the mixture subjected to the second drying into a plasma sintering furnace for spark plasma sintering, heating to 1300-1500 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 4-6min, wherein the pressure in the plasma sintering furnace is 30-50 MPa.

In an embodiment of the invention, the zirconium diboride-based cermet composite material uses zirconium diboride as a hard phase and AlFeNiCoCr high-entropy alloy as a bonding phase.

In an embodiment of the present invention, it is,the average corrosion rate of the zirconium diboride-based cermet composite material in molten aluminum at the temperature of 700 ℃ is 0.89 multiplied by 10^-3-1.17×10^-3mm/h。

The preparation method of the zirconium diboride-based metal ceramic composite material resistant to molten aluminum corrosion disclosed by the embodiment of the invention has the following advantages or beneficial effects:

the invention mixes Al powder, Fe powder, Ni powder, Co powder and Cr powder to perform ball milling pretreatment and drying pretreatment to enable the mixture to be mechanically alloyed so as to obtain AlFeNiCoCr high-entropy alloy powder, and the AlFeNiCoCr high-entropy alloy powder and zirconium diboride powder are mixed to prepare the zirconium diboride-based cermet composite material resistant to molten aluminum corrosion by a discharge plasma sintering method. By adopting spark plasma sintering, compact materials can be obtained at a lower sintering temperature, the time required by sintering can be greatly shortened, and the production efficiency and the compactness of the metal ceramic composite material are improved. The zirconium diboride-based cermet composite material obtained by the invention takes AlFeNiCoCr high-entropy alloy as a bonding phase, ZrB₂As the hard phase, the situation that the traditional metal ceramic material is easily corroded by molten aluminum by taking Co, Ni and other simple substances as binding phases is improved by utilizing the high entropy effect of the high entropy alloy, and the ZrB₂As the hard phase has the characteristics of high melting point, high hardness and the like, the corrosion performance of the molten aluminum of the zirconium diboride-based cermet composite material is better improved, and the service life of the composite material is longer. ZrB used in the invention₂The raw materials such as powder, Fe powder, Al powder, Cr powder and the like are common raw materials, so that the cost of the metal ceramic material can be effectively reduced. In addition, the preparation method is simple, the cost is low, and the corrosion resistance in the molten aluminum has very important engineering application value.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic flow chart of a method for preparing a metal ceramic composite according to an embodiment of the present invention;

FIG. 2 is an XRD pattern of ZrB2-12 wt.% AlFeNiCoCr cermet composite, ZrB2-20 wt.% AlFeNiCoCr cermet composite, ZrB2-30 wt.% AlFeNiCoCr cermet composite;

FIG. 3 is a cross-sectional morphology diagram of a ZrB 2-12% wtAlFeNiCoCr composite material under a scanning electron microscope;

FIG. 4 is a cross-sectional morphology diagram of a ZrB 2-20% wtAlFeNiCoCr composite material under a scanning electron microscope;

FIG. 5 is a cross-sectional morphology diagram of a ZrB 2-30% wtAlFeNiCoCr composite material under a scanning electron microscope;

FIG. 6 is a graphical representation of corrosion depth over time after aluminum liquid corrosion resistance for ZrB2-12 wt.% AlFeNiCoCr cermet composites, ZrB2-20 wt.% AlFeNiCoCr cermet composites, ZrB2-30 wt.% AlFeNiCoCr cermet composites samples;

FIG. 7 is a scanning electron microscope image of the ZrB 2-20% wtAlFeNiCoCr composite material after being resistant to aluminum liquid corrosion for 4, 8, 12 and 16 days.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific implementation, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

As shown in fig. 1, the present invention provides a method for preparing a zirconium diboride-based cermet composite material resistant to corrosion by molten aluminum, for example, comprising:

s11: putting Al powder, Fe powder, Ni powder, Co powder and Cr powder which respectively have preset mass percentages into a ball mill to carry out first ball milling process treatment to obtain a first ball milled mixture.

S12: and carrying out first vacuum drying process treatment on the mixture subjected to the first ball milling to obtain AlFeNiCoCr high-entropy alloy powder.

S13: and performing second ball milling process treatment on 70-88% by mass of zirconium diboride powder and 12-30% by mass of AlFeNiCoCr high-entropy alloy powder to obtain a second ball-milled mixture.

S14: and carrying out second vacuum drying process treatment on the second ball-milled mixture to obtain a second dried mixture.

S15: and performing discharge plasma sintering treatment on the second dried mixture to obtain the zirconium diboride-based cermet composite material.

Step S11 includes, for example: al, Fe, Ni, Co and Cr powder are mixed according to the mass percentage: 10.7% of Al powder, 22.1% of Fe powder, 23.3% of Ni powder, 23.3% of Co powder and 20.6% of Cr powder are weighed to obtain the high-entropy alloy raw material powder. Ball-milling pretreatment is carried out on high-entropy alloy powder, the high-entropy alloy raw material powder is filled into a stainless steel ball-milling tank of a ball mill, and the ball-material ratio is 10: 1 to 20: 1, and pouring 50-100ml of absolute ethyl alcohol to perform first ball milling process treatment to obtain a first ball milled mixture, wherein the rotation number of the ball mill is 200-.

Step S12 includes, for example: and putting the mixture subjected to the first ball milling into a vacuum drying oven to perform a first vacuum drying process treatment, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05-0.1 MPa.

Step S13 includes, for example: adding 70-88% of zirconium diboride powder and 12-30% of AlFeNiCoCr high-entropy alloy powder into a ball mill, wherein the ball-to-material ratio is 10: 1 to 20: 1, and adding 50-100ml of absolute ethyl alcohol to perform second ball milling process treatment to obtain a second ball-milled mixture, wherein the ball milling revolution is 200-300r/min, and the ball milling time is 5-10 h.

Step S14 includes, for example: and carrying out second vacuum drying process treatment on the mixture subjected to the second ball milling to obtain a second dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.1 MPa.

Step S15 includes, for example: and (3) performing discharge plasma sintering in the second dried mixture plasma sintering furnace, heating to 1300-1500 ℃ at the heating rate of 50 ℃/min, and keeping the temperature for 4-6min, wherein the pressure in the plasma sintering furnace is 30-50MPa, so as to obtain the zirconium diboride-based cermet composite material.

According to the embodiment of the invention, the AlFeNiCoCr high-entropy alloy powder is used as the binder phase, so that the condition that the traditional metal ceramic material is easily corroded by molten aluminum due to the fact that simple substances such as Co and Ni are used as the binder phase is improved; ZrB₂Has high temperature resistance, thermal shock resistance, high melting point and good high-temperature oxidation resistance, can be sintered at a lower temperature, and ZrB₂The corrosion resistance can be better improved by taking the hard phase as a hard phase; ZrB used in the examples of the invention₂The raw materials such as powder, Fe powder, Al powder, Cr powder and the like are common raw materials, so that the cost of the metal ceramic material can be effectively reduced; the preparation method is simple, the cost is low, and the corrosion resistance in the aluminum liquid has very important engineering application value.

Example 1

A preparation method of a metal ceramic composite material resistant to molten aluminum corrosion comprises the following steps:

step 1: mixing with ZrB₂And AlFeNiCoCr high entropy alloy mixed powder mass 40g, wherein ZrB₂The alloy is 88 percent by mass and 35.2g by mass, and the AlFeNiCoCr high-entropy alloy is 12 percent by mass and 4.8g by mass. Al powder, Fe powder, Ni powder, Co powder and Cr powder with the purity of 99.9 percent are mixed according to the mass percentage: weighing high-entropy alloy powder by using BL-200F electronic balance for Al 10.7%, Fe 22.1%, Ni 23.3%, Co 23.3% and Cr 20.6%, and weighing ZrB by using BL-200F electronic balance₂And (5) preparing powder for later use.

Step 2: and (3) performing first ball milling, namely filling the weighed high-entropy alloy powder into a stainless steel ball milling tank of a QM-3SP2 planetary ball mill, wherein the ball-to-feed ratio in the stainless steel ball milling tank is preferably 20: 1, pouring 50ml of absolute ethyl alcohol as a grinding aid to perform wet ball milling, wherein the ball milling time is 50 hours, and the ball milling revolution is 300r/min, so as to obtain a first ball-milled mixture.

And step 3: and (4) first vacuum drying, namely, filling the first ball-milled mixture obtained in the step S12 into an AYWZK-6030 vacuum drying oven, wherein the vacuum drying time is preferably 24 hours, the drying temperature is 90 ℃, and the vacuum degree is-0.1 MPa, so as to obtain a first dried mixture, namely AlFeNiCoCr high-entropy alloy powder.

And 4, step 4: a second ball milling step, namely screening the AlFeNiCoCr high-entropy alloy powder obtained in the step S13 through a 400-mesh screen, selecting AlFeNiCoCr high-entropy alloy powder with the average grain diameter of 5-45 mu m, and mixing 40g of ZrB₂And the AlFeNiCoCr high-entropy alloy mixed powder is added into a stainless steel ball-milling tank of a QM-3SP2 planetary ball mill, and preferably, the ball-material ratio is 10: 1, carrying out wet ball milling on a stainless steel ball with the diameter of 10mm and 50ml of absolute ethyl alcohol for 5 hours at the ball milling revolution of 300r/min to obtain a second ball-milled mixture.

And 5: and (4) second vacuum drying, namely filling the second ball-milled mixture obtained in the step S14 into an AYWZK-6030 vacuum drying oven for vacuum drying, wherein the time used in the vacuum drying process is preferably 24 hours, the drying temperature is 90 ℃, and the vacuum degree is-0.1 MPa, so as to obtain a second dried mixture.

Step 6: and (4) sintering, namely putting the obtained second dried mixture obtained in the step S15 into a graphite mold of an SPS-1050Rx discharge plasma sintering furnace for discharge plasma sintering, wherein the sintering temperature is 1400 ℃, the heat preservation time is 5min, the applied pressure is 50MPa, and the temperature rising speed is 50 ℃/min.

ZrB is obtained after sintering₂-12 wt.% AlFeNiCoCr cermet composite, example 2

A preparation method of a metal ceramic composite material resistant to molten aluminum corrosion comprises the following steps:

step 1: mixing with ZrB₂And AlFeNiCoCr high entropy alloy mixed powder mass 40g, wherein ZrB₂The alloy is 80 percent by mass and 32g by mass, and the AlFeNiCoCr high-entropy alloy is 20 percent by mass and 8g by mass. Al powder, Fe powder, Ni powder, Co powder and Cr powder with the purity of 99.9 percent are mixed according to the mass percentage: al 10.7%, Fe 22.1%, Ni 23.3%, Co 23.3%, Cr 20.6% are weighed by BL-200F electronic balanceTaking high-entropy alloy powder, and weighing ZrB by using a BL-200F electronic balance₂And (5) preparing powder for later use.

Step 2: and (3) performing first ball milling, namely filling the weighed high-entropy alloy powder into a stainless steel ball milling tank of a QM-3SP2 planetary ball mill, wherein the ball-to-feed ratio in the stainless steel ball milling tank is preferably 20: 1, pouring 50ml of absolute ethyl alcohol as a grinding aid to perform wet ball milling, wherein the ball milling time is 65 hours, and the ball milling revolution is 250r/min, so as to obtain a first ball-milled mixture.

And step 3: and (4) first vacuum drying, namely, filling the first ball-milled mixture obtained in the step S12 into an AYWZK-6030 vacuum drying oven, wherein the vacuum drying time is preferably 23h, the drying temperature is 95 ℃, and the vacuum degree is-0.08 MPa, so that a first dried mixture, namely AlFeNiCoCr high-entropy alloy powder is obtained.

And 4, step 4: a second ball milling step, namely screening the AlFeNiCoCr high-entropy alloy powder obtained in the step S13 through a 400-mesh screen, selecting AlFeNiCoCr high-entropy alloy powder with the average grain diameter of 5-45 mu m, and mixing 40g of ZrB₂And the AlFeNiCoCr high-entropy alloy mixed powder is added into a stainless steel ball-milling tank of a QM-3SP2 planetary ball mill, and preferably, the ball-material ratio is 10: 1, carrying out wet ball milling on a stainless steel ball with the diameter of 10mm and 75ml of absolute ethyl alcohol for 8 hours at the ball milling revolution of 250r/min to obtain a second ball-milled mixture.

And 5: and (4) second vacuum drying, namely filling the second ball-milled mixture obtained in the step S14 into an AYWZK-6030 vacuum drying oven for vacuum drying, wherein the time used in the vacuum drying process is preferably 23h, the drying temperature is 95 ℃, and the vacuum degree is-0.08 MPa, so as to obtain a second dried mixture.

Step 6: and (4) sintering, namely putting the obtained second dried mixture obtained in the step S15 into a graphite mold of an SPS-1050Rx discharge plasma sintering furnace for discharge plasma sintering, wherein the sintering temperature is preferably 1300 ℃, the heat preservation time is preferably 6min, the applied pressure is preferably 30MPa, and the temperature rising speed is preferably 50 ℃/min.

ZrB is obtained after sintering₂-20 wt.% AlFeNiCoCr cermet composite。

Example 3

A preparation method of a metal ceramic composite material resistant to molten aluminum corrosion comprises the following steps:

step 1: mixing with ZrB₂And AlFeNiCoCr high entropy alloy mixed powder mass 40g, wherein ZrB₂The alloy is 70 percent by mass and 28g by mass, and the AlFeNiCoCr high-entropy alloy is 30 percent by mass and 12g by mass. Al powder, Fe powder, Ni powder, Co powder and Cr powder with the purity of 99.9 percent are mixed according to the mass percentage: weighing 10.7% of Al, 22.1% of Fe, 23.3% of Ni, 23.3% of Co and 20.6% of Cr by using a BL-200F electronic balance, and weighing ZrB by using the BL-200F electronic balance₂And (5) preparing powder for later use.

Step 2, first ball milling, namely filling the weighed high-entropy alloy powder into a stainless steel ball milling tank of a QM-3SP2 planetary ball mill, preferably, adding a mixture of 20: 1, pouring 100ml of absolute ethyl alcohol as a grinding aid into stainless steel balls with the diameter of 10mm, and performing wet ball milling for 80 hours at the ball milling revolution of 200r/min to obtain a first ball-milled mixture.

And step 3: and (3) performing first vacuum drying, namely filling the first ball-milled mixture obtained in the step (2) into an AYWZK-6030 vacuum drying oven, wherein the vacuum drying time is preferably 22 hours, the drying temperature is 100 ℃, and the vacuum degree is-0.05 MPa, so as to obtain a first dried mixture, namely AlFeNiCoCr high-entropy alloy powder.

And 4, step 4: and a second ball milling step, namely screening the AlFeNiCoCr high-entropy alloy powder obtained in the step 3 by using a 400-mesh screen, selecting AlFeNiCoCr high-entropy alloy powder with the average grain diameter of 5-45 mu m, and mixing 40g of ZrB₂And the AlFeNiCoCr high-entropy alloy mixed powder is added into a stainless steel ball-milling tank of a QM-3SP2 planetary ball mill, and preferably, the ball-material ratio is 10: 1, carrying out wet ball milling on a stainless steel ball with the diameter of 10mm and 100ml of absolute ethyl alcohol for 10 hours at the ball milling revolution of 200r/min to obtain a second ball-milled mixture.

And 5: and (3) second vacuum drying, namely filling the second ball-milled mixture obtained in the step (4) into an AYWZK-6030 vacuum drying oven for vacuum drying, wherein the time used in the vacuum drying process is preferably 22 hours, the drying temperature is 100 ℃, and the vacuum degree is-0.05 MPa, so as to obtain a second dried mixture.

Step 6: and (3) sintering, namely putting the second dried mixture obtained in the step (5) into a graphite mold of an SPS-1050Rx discharge plasma sintering furnace for discharge plasma sintering, wherein preferably, the sintering temperature is 1500 ℃, the heat preservation time is 4min, the applied pressure is 40MPa, and the temperature rising speed is 50 ℃/min.

ZrB is obtained after sintering₂-30 wt.% AlFeNiCoCr cermet composite.

ZrB of the present invention obtained, for example, in example 1, example 2 and example 3₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-30 wt.% of AlFeNiCoCr cermet composite was sampled for compositional and microscopic appearance observations.

See FIG. 2, which is ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-XRD pattern of 30 wt.% AlFeNiCoCr cermet composite sample. The solid solution with a simple structure formed after the AlFeNiCoCr high-entropy alloy is mechanically alloyed is BCC single-phase solid solution, and when the content of the AlFeNiCoCr high-entropy alloy is increased, ZrB₂The diffraction peak position of BCC single-phase solid solution of AlFeNiCoCr high-entropy alloy in the XRD pattern of the AlFeNiCoCr composite material is increased.

Specifically, ZrB is shown in FIGS. 3-5 respectively₂-12 wt.% of an AlFeNiCoCr cermet composite sample, ZrB₂-20 wt.% of an AlFeNiCoCr cermet composite sample, ZrB₂A cross-sectional morphology of a 30 wt.% AlFeNiCoCr cermet composite sample under a scanning electron microscope, and it can be seen from the figure that as the content of the AlFeNiCoCr high-entropy alloy increases, the AlFeNiCoCr high-entropy alloy enters ZrB₂Gap-filling of sintered body, ZrB₂-increased compactness of the AlFeNiCoCr cermet composite material.

It is worth mentioning that the inventionAlso to ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-30 wt.% of AlFeNiCoCr metal ceramic composite material sample is subjected to a molten aluminum corrosion resistance test.

The cermet composite material sample obtained by sintering was cut by a wire electric discharge machine to obtain a plurality of rectangular test pieces of 5mm × 5mm × 12 mm. The surface of the rectangular test piece was polished with sandpaper, the oxide film on the surface of the rectangular test piece was removed, and the thickness of the sample before etching was measured by a micrometer. Placing the rectangular sample into a graphite crucible filled with 700 ℃ aluminum liquid for corrosion experiment, heating and preserving heat through a well-type resistance furnace, respectively corroding the rectangular sample for 4 days, 8 days, 12 days and 16 days, taking out and cooling, and analyzing ZrB by using a Scanning Electron Microscope (SEM)₂The texture of the corrosion interface of the AlFeNiCoCr metal ceramic composite material and the aluminum liquid, the dimension and thickness of the rectangular sample after corrosion are measured by using SmileView software, and the chemical composition of the phase is measured by using an energy spectrometer (EDS).

In the experiment, the corrosion rate is measured by a depth method, and the calculation formula is as follows: v ═ a-b)/2 t.

Wherein a is the thickness of the sample before corrosion, b is the thickness of the sample after corrosion, t is corrosion time, the thickness a before corrosion is accurately measured by a micrometer before a corrosion experiment, then the structural observation is carried out on the general appearance of the cross section of the sample after corrosion under a scanning electron microscope, and the residual thickness b of the sample after corrosion is measured by SmileView software.

FIG. 6 is ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-30 wt.% AlFeNiCoCr metal ceramic composite material corrosion depth with time after resisting aluminum liquid corrosion. As can be seen from the graph, the etch depth exhibits a uniform linear increase as the etch time increases, according to the above calculation: the specific corrosion rate was calculated when v ═ a-b)/2 t: ZrB₂Average Corrosion Rate of-12% HEAs 0.89X 10^-3mm/h，ZrB₂Average Corrosion Rate of-20% HEAs 1.02X 10^-3mm/h，ZrB₂Average corrosion rate of 30% HEAsIs 1.17X 10^-3mm/h. Compared with the corrosion rate of cast iron in molten aluminum of 0.85mm/h, the metal ceramic material obtained by the invention has greatly improved molten aluminum corrosion resistance.

In FIG. 7, a-d are sequentially ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-30 wt.% AlFeNiCoCr cermet composite material against molten aluminum corrosion after 4, 8, 12, 16 days. The aluminum layer, the corrosion layer and the substrate are arranged from top to bottom in sequence. From the picture after 4 days of corrosion, it can be found that the aluminum liquid starts to corrode the substrate, and in the experiment, as the corrosion days of the aluminum liquid increase, the aluminum liquid preferentially corrodes the high-entropy alloy to slowly increase the depth of the corrosion layer, but the corrosion layer is not separated from the substrate of the material and is dissociated in the aluminum liquid, so that the material still has good corrosion resistance and remains complete.

It is worth mentioning that ZrB₂Has high temperature resistance, thermal shock resistance, high melting point and good high-temperature oxidation resistance, and can be sintered at a lower temperature. The AlFeNiCoCr high-entropy alloy is used as a binding phase, a simple solid solution structure can be formed, and the AlFeNiCoCr high-entropy alloy powder after mechanical alloying has good chemical uniformity and fine grain size, so that the corrosion resistance and the wear resistance of a coating formed by spraying and a composite material formed by sintering are further improved. Therefore, the metal ceramic composite coating and the metal ceramic composite material which use the high-entropy alloy as the binding phase can prolong the service life of hot-dip aluminum plating equipment and have good promotion effect on the development of the aluminum industry.

In summary, the invention provides a preparation method of a zirconium diboride-based cermet composite material resistant to corrosion of molten aluminum, which comprises the steps of mixing Al powder, Fe powder, Ni powder, Co powder and Cr powder, carrying out ball-milling pretreatment and drying pretreatment to mechanically alloy the mixture so as to obtain AlFeNiCoCr high-entropy alloy powder, mixing the AlFeNiCoCr high-entropy alloy powder and ZrB2 powder, and preparing the zirconium diboride-based cermet composite material resistant to corrosion of molten aluminum by a spark plasma sintering method. By adopting spark plasma sintering, compact materials can be obtained at a lower sintering temperature, the time required by sintering can be greatly shortened, and the production efficiency and the compactness of the metal ceramic composite material are improved. The zirconium diboride-based cermet composite material obtained by the invention takes AlFeNiCoCr high-entropy alloy as a bonding phase and ZrB2 as a hard phase, and utilizes the high-entropy effect of the high-entropy alloy to improve the condition that the traditional cermet material is easy to be corroded by molten aluminum because the simple substances such as Co, Ni and the like are taken as the bonding phase, and ZrB2 as the hard phase has the characteristics of high melting point, high hardness and the like, so that the molten aluminum corrosion performance and the service life of the zirconium diboride-based cermet composite material are better improved. In addition, the ZrB2 powder, the Fe powder, the Al powder, the Cr powder and other raw materials used in the invention are common raw materials, so that the cost of the cermet material can be effectively reduced. In addition, the preparation method is simple, the cost is low, and the corrosion resistance in the molten aluminum has very important engineering application value.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.