阅读说明：本技术 耐铝液腐蚀的金属陶瓷复合材料、粉末及其涂层、沉没辊 (Aluminum liquid corrosion resistant metal ceramic composite material, powder, coating of powder and sink roller ) 是由 尹冰冰 任可柱 尹付成 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铝液腐蚀的金属陶瓷复合材料、粉末及其涂层以及一种沉没辊,所述金属陶瓷复合材料以ZrB-2粉、AlFeNiCoCr高熵合金粉末为原料,其中所述原料的质量百分比计的组分构成为：ZrB-2粉末70％-88％,AlFeNiCoCr高熵合金粉末12％-30％,其中AlFeNiCoCr高熵合金粉末中Al粉、Fe粉、Ni粉、Co粉、Cr粉分别为Al粉10.7％、Fe粉22.1％、Ni粉23.3％、Co粉23.3％、Cr粉20.6％；并且所述金属陶瓷复合材料以ZrB-2为硬质相,AlFeNiCoCr高熵合金为粘结相,具有优异的耐铝液腐蚀性能,且制作方法简单,成本低廉,在工业应用中有良好的前景。(The embodiment of the invention discloses a molten aluminum corrosion resistant metal ceramic composite material, powder and a coating thereof, and a sink roll, wherein the metal ceramic composite material is formed by ZrB 2 The alloy powder comprises the following components in percentage by mass: ZrB 2 70-88% of powder and 12-30% of AlFeNiCoCr high-entropy alloy powder, wherein Al powder, Fe powder, Ni powder and Co powder in the AlFeNiCoCr high-entropy alloy powderThe Cr powder is 10.7 percent of Al powder, 22.1 percent of Fe powder, 23.3 percent of Ni powder, 23.3 percent of Co powder and 20.6 percent of Cr powder respectively; and the metal ceramic composite material is formed by ZrB 2 The alloy is a hard phase, the AlFeNiCoCr high-entropy alloy is a binding phase, the alloy has excellent aluminum liquid corrosion resistance, the manufacturing method is simple, the cost is low, and the alloy has good prospects in industrial application.)

1. The metal ceramic composite material resistant to aluminum liquid corrosion is characterized in that ZrB is adopted as the metal ceramic composite material₂Hard phase, AlFeNiCoCr high entropy alloy as binding phase; the metal ceramic composite material is ZrB₂The powder and the AlFeNiCoCr high-entropy alloy powder are used as raw materials and are prepared by a wet ball milling process, a vacuum drying process and a plasma sintering process;

the raw materials comprise the following components in percentage by mass: ZrB₂70-88% of powder and 12-30% of AlFeNiCoCr high-entropy alloy powder; the mass percentages of Al powder, Fe powder, Ni powder, Co powder and Cr powder in the AlFeNiCoCr high-entropy alloy powder are respectively 10.7% of Al, 22.1% of Fe, 23.3% of Ni, 23.3% of Co and 20.6% of Cr;

wherein, the wet ball milling process comprises the following steps: reacting the ZrB₂Putting the powder and the AlFeNiCoCr high-entropy alloy powder into a ball mill, adding absolute ethyl alcohol to perform wet ball milling to obtain a ball-milled mixture, wherein the ball milling time is 5-10h, and the ball milling revolution is 200-300 r/min;

wherein the vacuum drying process comprises the following steps: putting the ball-milled mixture into a vacuum drying oven for vacuum drying to obtain a dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05 to-0.1 MPa;

wherein the plasma sintering process comprises: placing the dried mixture into a plasma sintering furnace for spark plasma sintering, wherein the sintering temperature is 1300-1500 ℃, the heat preservation time is 4-6min, the pressure is 30-50MPa, and the heating speed is 50 ℃/min;

wherein the average corrosion rate of the metal ceramic composite material in molten aluminum at the temperature of 700 ℃ is 0.89 multiplied by 10^-3-1.17×10^-3mm/h。

2. The metal ceramic composite material resistant to aluminum liquid corrosion is characterized in that ZrB is adopted as the metal ceramic composite material₂Is a hard phase, AlFeNiCoCr high-entropy alloy is a binding phase and ZrB is used₂The powder and AlFeNiCoCr high-entropy alloy powder are used as raw materials; the raw materials comprise the following components in percentage by mass: ZrB₂70-88% of powder and 12-30% of AlFeNiCoCr high-entropy alloy powder; wherein the mass percentages of Al powder, Fe powder, Ni powder, Co powder and Cr powder in the AlFeNiCoCr high-entropy alloy powder are respectively 10.7 percent of Al powder, 22.1 percent of Fe powder and 23.3 percent of Ni powder23.3 percent of Co powder and 20.6 percent of Cr powder.

3. The cermet composite of claim 2, characterised in that the cermet composite has an average corrosion rate of 0.89 x 10 in a molten aluminium liquid at a temperature of 700 ℃^-3-1.17×10^-3mm/h。

4. The cermet composite material according to claim 2, wherein the AlFeNiCoCr high-entropy alloy powder is prepared from the Al powder, the Fe powder, the Ni powder, the Co powder and the Cr powder through a first ball milling process and a first vacuum drying process;

wherein the first ball milling process comprises: and (2) putting the Al powder, the Fe powder, the Ni powder, the Co powder and the Cr powder into a ball mill, and adding a material-ball ratio of 10: 1-20: 1, introducing absolute ethyl alcohol into the stainless steel ball, and performing wet ball milling 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;

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.

5. The cermet composite material of claim 2 resistant to molten aluminum corrosion, characterized in that the cermet composite material is formed by ZrB₂The powder and the AlFeNiCoCr high-entropy alloy powder are prepared by a second ball milling process, a second vacuum drying process and a sintering process.

6. The cermet composite of claim 5, wherein the second ball milling process comprises: reacting the ZrB₂And (2) putting the 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 is added with 50ml of absolute ethyl alcohol for wet ball milling to obtainAfter the second ball milling, the ball milling time of the mixture is 5-10h, and the ball milling revolution is 200-300 r/min;

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 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.

7. The cermet composite material with molten aluminum corrosion resistance of claim 6, 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.

8. Cermet powder resistant to molten aluminum corrosion, characterized in that it is prepared from a cermet composite according to any of claims 1-7 by a third ball milling process.

9. A cermet coating resistant to molten aluminum corrosion, characterized in that the cermet coating is prepared from the cermet composite powder of claim 8 by a spray coating process.

10. The sink roll is characterized by comprising a roll body, wherein the roll body comprises:

a substrate;

a cermet coating of a cermet composite material according to any one of claims 1-7 or of a cermet coating of a cermet powder according to claim 8 or of a cermet coating according to claim 9 on a surface of said substrate.

Technical Field

The invention belongs to the field of metal ceramic materials, and particularly relates to aluminum liquid corrosion resistant metal ceramic powder, an aluminum liquid corrosion resistant metal ceramic coating, an aluminum liquid corrosion resistant metal ceramic composite material and a sink roll.

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 more active, and the molten aluminum is one of the most corrosive molten metals, so the hot dip aluminum plating technology has the defect that the hot dip aluminum plating technology cannot avoid the molten aluminum melt, and the molten aluminum melt has great corrosivity for hot dip aluminum plating equipment, so that equipment such as a sink roll in a hot dip aluminum plating production line is permeated by molten aluminum to generate aluminum slag and pitting corrosion, so that the quality of a hot dip aluminum plated layer is poor, the service life of the hot dip aluminum plating equipment is shortened, and the problem of aluminum liquid corrosion resistance of hot dip aluminum plating equipment materials is greatly influenced for the development of the aluminum industry.

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 embodiment of the invention mainly aims to overcome the defects and shortcomings of the prior art, and provides the aluminum liquid corrosion resistant metal ceramic powder, the aluminum liquid corrosion resistant metal ceramic coating, the aluminum liquid corrosion resistant metal ceramic composite material and the sink roller, which have excellent aluminum liquid corrosion resistance.

The embodiment of the invention discloses a metal ceramic composite material resisting aluminum liquid corrosion, which uses Zr as a raw materialB₂Hard phase, AlFeNiCoCr high entropy alloy as binding phase; the metal ceramic composite material is ZrB₂The powder and the AlFeNiCoCr high-entropy alloy powder are used as raw materials and are prepared by a wet ball milling process, a vacuum drying process and a plasma sintering process. The raw materials comprise the following components in percentage by mass: ZrB₂70-88% of powder and 12-30% of AlFeNiCoCr high-entropy alloy powder; the mass percentages of Al powder, Fe powder, Ni powder, Co powder and Cr powder in the AlFeNiCoCr high-entropy alloy powder are respectively 10.7% of Al, 22.1% of Fe, 23.3% of Ni, 23.3% of Co and 20.6% of Cr. The wet ball milling process comprises the following steps: reacting the ZrB₂And putting the powder and the AlFeNiCoCr high-entropy alloy powder into a ball mill, adding absolute ethyl alcohol to perform wet ball milling to obtain a ball-milled mixture, wherein the ball milling time is 5-10h, and the ball milling revolution is 200-300 r/min. The vacuum drying process comprises the following steps: and putting the ball-milled mixture into a vacuum drying oven for vacuum drying to obtain a dried mixture, wherein the drying time is 22-24h, the drying temperature is 90-100 ℃, and the vacuum degree is-0.05 to-0.1 MPa. The plasma sintering process comprises the following steps: and (3) putting the dried mixture into a plasma sintering furnace for spark plasma sintering, wherein the sintering temperature is 1300-1500 ℃, the heat preservation time is 4-6min, the pressure is 30-50MPa, and the heating speed is 50 ℃/min. The average corrosion rate of the metal ceramic composite material in molten aluminum at the temperature of 700 ℃ is 8.93 multiplied by 10^-3-1.17×10^-3mm/h。

In one embodiment of the invention, the cermet composite material is ZrB₂Is a hard phase, AlFeNiCoCr high-entropy alloy is a binding phase and ZrB is used₂The powder and AlFeNiCoCr high-entropy alloy powder are used as raw materials; the raw materials comprise the following components in percentage by mass: ZrB₂70-88% of powder and 12-30% of AlFeNiCoCr high-entropy alloy powder; the Al powder, the Fe powder, the Ni powder, the Co powder and the Cr powder in the AlFeNiCoCr high-entropy alloy powder are respectively 10.7% by mass, 22.1% by mass, 23.3% by mass and 20.6% by mass.

In one embodiment of the invention, the cermet composite has an average corrosion in a molten aluminum bath at a temperature of 700 DEG CThe etching rate is 8.93 x 10^-3-1.17×10^-3mm/h。

In an embodiment of the invention, the AlFeNiCoCr high-entropy alloy powder is prepared from the Al powder, the Fe powder, the Ni powder, the Co powder, and the Cr powder through a first ball milling process and a first vacuum drying process. Wherein the first ball milling process comprises: and (2) 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-material ratio of 10: 1-20: 1, introducing absolute ethyl alcohol into the stainless steel ball, and performing wet ball milling 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. 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 one embodiment of the invention, the cermet composite is formed from the ZrB₂The powder and the AlFeNiCoCr high-entropy alloy powder are prepared by a second ball milling process, a second vacuum drying process and a sintering process.

In one embodiment of the present invention, the second ball milling process comprises: reacting the ZrB₂And (2) putting the 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. 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 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 one 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.

The invention also discloses aluminum liquid corrosion resistant metal ceramic powder, which is characterized in that the metal ceramic powder is prepared from the metal ceramic composite material by a third ball milling process.

The other embodiment of the invention also discloses a molten aluminum corrosion resistant metal ceramic coating, which is prepared by spraying the metal ceramic composite powder.

The invention also discloses a sink roll resistant to aluminum liquid corrosion, which comprises a roll body, wherein the roll body comprises: a substrate; a cermet coating made of a cermet composite material as described previously, or a cermet coating made of a cermet powder as described previously, or a cermet coating as described previously, wherein the cermet coating is located on the surface of the substrate.

The aluminum liquid corrosion resistant metal ceramic powder, the coating and the composite material thereof and the sink roll disclosed by the embodiment of the invention have the following advantages or beneficial effects:

(1) 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; (2) 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; (3) ZrB for use 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; (4) the preparation method is simple, the cost is low, and the corrosion resistance in the aluminum liquid 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 ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂-XRD pattern of 30 wt.% AlFeNiCoCr cermet composite;

FIG. 3 is ZrB₂-a cross-sectional topography under a scanning electron microscope of 12% wtAlFeNiCoCr composite material;

FIG. 4 is ZrB₂-a cross-sectional topography under a scanning electron microscope of 20% wtAlFeNiCoCr composite material;

FIG. 5 is ZrB₂-a cross-sectional topography under a scanning electron microscope of 30% wtAlFeNiCoCr composite material;

FIG. 6 is ZrB₂-12 wt.% AlFeNiCoCr cermet composite, ZrB₂-20 wt.% of AlFeNiCoCr cermet composite, ZrB₂A schematic diagram of the corrosion depth of a 30 wt.% AlFeNiCoCr cermet composite sample after being resistant to molten aluminum corrosion as a function of time;

FIG. 7 is ZrB₂-20% wtalFeNiCoCr composite material is resistant to aluminium liquid corrosion for 4, 8, 12 and 16 days;

fig. 8 is a schematic structural diagram of a sink roll according to an embodiment of the present invention.

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 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: 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 ZrB₂Mixed with AlFeNiCoCr high entropy alloyThe mass of the powder is 40g, in which 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: 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: 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 ZrB₂Adding AlFeNiCoCr high-entropy alloy powder and AlFeNiCoCr high-entropy alloy mixed powder into QM-3SP2 planetary ball milling ball millIn the stainless steel ball milling tank of the machine, 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, ZrB₂-30 wt.% AlFeNiCoCr cermet compositionThe cross-sectional morphology of the composite material sample under a scanning electron microscope can be seen from the figure, along with the increase of the content of the AlFeNiCoCr high-entropy alloy, the AlFeNiCoCr high-entropy alloy enters the ZrB₂Gap-filling of sintered body, ZrB₂-increased compactness of the AlFeNiCoCr cermet composite material.

It is worth mentioning that the invention also deals with 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 figure, as the decay progressesThe etching time is increased, the etching depth is uniformly and linearly increased, and the calculation formula is as follows: 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% HEAs 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.

Example 4

In addition, the embodiment of the invention also provides a preparation method of the metal ceramic powder resisting aluminum liquid corrosion, which comprises the following steps:

step 1: and carrying out third ball milling process treatment on the metal ceramic composite material to obtain a third ball milled mixture, wherein the third ball milling process is the same as the second ball milling process.

Step 2: and carrying out a third vacuum drying process on the mixture subjected to the third ball milling to obtain metal ceramic powder, wherein the third vacuum drying process is the same as the second vacuum drying process.

ZrB can be obtained by the steps₂-12wt.％AlFeNiCoCr、ZrB₂-20wt.％AlFeNiCoCr、ZrB₂-30 wt.% AlFeNiCoCr cermet powder.

Example 5

In addition, the embodiment of the invention also provides a preparation method of the aluminum liquid corrosion resistant metal ceramic coating, which comprises the following steps: the method comprises the following steps:

step 1: the metal ceramic powder is subjected to a spraying process, namely the metal ceramic powder is sprayed on a substrate by adopting an active combustion high-speed gas spraying process to obtain a metal ceramic coating, wherein the substrate can be 316L stainless steel.

ZrB can be obtained by the steps₂-12wt.％AlFeNiCoCr、ZrB₂-20wt.％AlFeNiCoCr、ZrB₂-30 wt.% AlFeNiCoCr cermet coating.

It is worth mentioning that the active combustion high-speed gas spraying process is a supersonic flame spraying technology, and is characterized in that high-speed airflow is generated by burning compressed air and fuel to heat powder, but the powder is not completely melted, and the powder is accelerated to be more than 700m/s and impacts a substrate to form a coating with extremely low oxide content and extremely high density.

Example 6

As shown in fig. 8, an embodiment of the present invention also provides a sink roll 100. Sink roll 100 includes a roll body 110. The roll body 110 includes a base 111 and a cermet coating 112. The roller body 110 may be cylindrical, for example, but may also be cylindrical or have other shapes. The material of the substrate 111 may be stainless steel, such as 316L stainless steel. The cermet coating 112 is disposed on the surface of the substrate 111. The cermet coating 112 may be applied to the surface of the substrate 111 by, for example, an active combustion high velocity gas spray process for improving corrosion resistance and oxidation resistance of the sink roll 10. The cermet coating 112 may be a cermet coating in the previous embodiment, or a cermet coating made of a cermet powder in the previous embodiment, or a cermet coating made of a cermet material in the previous embodiment. Further, the sink roll 100 further includes roll shafts 120 disposed at both ends of the roll body 110.

In conclusion, the embodiment of the invention provides the aluminum liquid corrosion resistant metal ceramic powder, the coating, the composite material of the metal ceramic powder and the coating and the sink roller, and the AlFeNiCoCr high-entropy alloy powder is used as the bonding phase, so that the condition that the traditional metal ceramic material is easily corroded by aluminum liquid due to the fact that simple substances such as Co, Ni and the like are used as the bonding phase is improved; ZrB₂The high-temperature-resistant and high-shock-resistant ceramic material has high temperature resistance, high melting point and good high-temperature oxidation resistance, can be sintered at a lower temperature, and can better improve the corrosion resistance by taking ZrB2 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; and the manufacturing method is simple, the cost is low, and the corrosion resistance in the aluminum liquid 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.