阅读说明：本技术 一种TiB2-FeCoNiCrMn耐铝液腐蚀材料 (TiB2-FeCoNiCrMn aluminum liquid corrosion resistant material ) 是由 尹冰冰 高志栋 尹付成 王鑫铭 易华清 任可柱 于 2020-12-07 设计创作，主要内容包括：本发明实施例公开了一种TiB-2-FeCoNiCrMn耐铝液腐蚀材料,由TiB-2粉和FeCoNiCrMn高熵合金粉末经球磨、干燥、烧结后而成,其中FeCoNiCrMn高熵合金粉末以Fe粉、Co粉、Ni粉、Cr粉、Mn粉为原料经机械合金化而成。该TiB-2-FeCoNiCrMn耐铝液腐蚀材料易于制备,具有优异的抗铝液腐蚀特性。(The embodiment of the invention discloses a TiB 2 -FeCoNiCrMn aluminum liquid corrosion resistant material composed of TiB 2 The powder and FeCoNiCrMn high-entropy alloy powder are formed by ball milling, drying and sintering, wherein the FeCoNiCrMn high-entropy alloy powder is formed by mechanically alloying Fe powder, Co powder, Ni powder, Cr powder and Mn powder serving as raw materials. The TiB 2 The FeCoNiCrMn aluminum liquid corrosion resistant material is easy to prepare and has excellent aluminum liquid corrosion resistance.)

1. TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized by that, it is made of TiB₂The powder and FeCoNiCrMn high-entropy alloy powder are formed by ball milling, drying and sintering; wherein the TiB₂The mass percent of the powder is 70-88%, and the mass percent of the FeCoNiCrMn high-entropy alloy powder is 12-30%.

2. The TiB of claim 1₂The FeCoNiCrMn aluminum liquid corrosion resistant material is characterized in that the FeCoNiCrMn high-entropy alloy powder is formed by mechanically alloying Fe powder, Co powder, Ni powder, Cr powder and Mn powder serving as raw materials;

the mechanical alloying is to put Fe powder, Co powder, Ni powder, Cr powder and Mn powder in equal molar ratio into a ball milling tank, ball milling is carried out by adopting a wet method, a proper amount of absolute ethyl alcohol is poured, the ball-material ratio is 5:1, the rotating speed is 200-300 r/min, the ball milling time is 50-60 hours, and the mechanical alloying is stopped for half an hour every 4 hours; and then putting the ball-milled powder into a vacuum drying oven for drying, wherein the drying temperature is 70-90 ℃, the vacuum degree is-0.07 MPa-0.1 MPa, and the drying time is 8-12 hours.

3. The TiB of claim 2₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that the raw material of FeCoNiCrMn high entropy alloy powder is in the TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following components in percentage by mass:

2.39-5.98% of Fe powder, 2.52-6.30% of Co powder, 2.51-6.28% of Ni powder, 2.23-5.56% of Cr powder and 2.35-5.88% of Mn powder.

4. According to claimTiB as described in claim 1₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that said TiB₂The purity of the powder is 99.5-99.9%, and the particle size is 2-5 microns.

5. The TiB of claim 2₂The aluminum liquid corrosion resistant material FeCoNiCrMn is characterized in that the purity of the Fe powder, the purity of the Co powder, the purity of the Ni powder, the purity of the Cr powder and the purity of the Mn powder are 99.9-99.99%, and the particle size of the Cr powder and the Mn powder is 5-10 micrometers.

6. The TiB of claim 2₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that said TiB₂Is powdered on the TiB₂The mass percentage of the-FeCoNiCrMn aluminum liquid corrosion resistant material is 80-88%.

7. The TiB of claim 6₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that the raw material of FeCoNiCrMn high entropy alloy powder is in the TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following components in percentage by mass:

2.39-3.98% of Fe powder, 2.52-4.20% of Co powder, 2.51-4.19% of Ni powder, 2.23-3.71% of Cr powder and 2.35-3.92% of Mn powder.

8. The TiB of claim 1₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that said TiB₂The densification degree of the FeCoNiCrMn aluminum liquid corrosion resistant material is 94.1-98.6%, and the macro hardness is 51.24-74.36 HRC.

9. The TiB of claim 1₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that the sintering is spark plasma sintering.

10. The TiB of claim 9₂-FeCoNiCrMn aluminum liquid corrosion resistant material, characterized in that the spark plasma sintering refers to: packaging the dried powder inIn the mold, the temperature is raised to a temperature T at a temperature raising rate of 200-300 ℃, the temperature T is 1400-1500 ℃, the temperature is kept for 5-10 minutes in the environment of the temperature T, and the pressure is 50-60 Mpa.

Technical Field

The invention relates to the field of aluminum liquid corrosion resistant materials, in particular to a TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material.

Background

At present, aluminum and its alloy are widely used in the fields of traffic, energy, electronics, etc. But the aluminum liquid is one of the most corrosive metal liquids, so that equipment directly contacting the aluminum liquid is greatly corroded in a smelting, casting and hot-dip aluminizing production line, and the service life of the equipment is greatly shortened. And the dissolution of the materials in the aluminum liquid may pollute the aluminum liquid, so that the product quality is low, and the production efficiency is influenced. In a hot-dip aluminum plating production line, equipment such as an aluminum liquid loading tank, an immersion roller and the like needs to be soaked in aluminum liquid for a long time, so that the service life of the hot-dip aluminum plating production equipment is shortened, the quality of a plating layer is reduced, the energy consumption is increased, the production efficiency is reduced and other adverse effects are caused. Therefore, the aluminum liquid corrosion resistance of the material is improved, and a series of corrosion problems such as aluminum liquid pollution, corrosion perforation of an aluminum liquid containing container, aluminum sticking of an aluminum forming die and the like can be effectively solved.

Therefore, a new material resistant to molten aluminum corrosion needs to be designed.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material, the TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material has excellent aluminum liquid corrosion resistance.

The technical solution of the invention is as follows:

TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material composed of TiB₂The powder and FeCoNiCrMn high-entropy alloy powder are subjected to ball milling, drying and sintering to obtain the alloy powder; wherein the TiB₂The mass percent of the powder is 70-88%, and the mass percent of the FeCoNiCrMn high-entropy alloy powder is 12-30%.

Further, the FeCoNiCrMn high-entropy alloy powder is formed by mechanically alloying Fe powder, Co powder, Ni powder, Cr powder and Mn powder serving as raw materials;

the mechanical alloying is to put Fe powder, Co powder, Ni powder, Cr powder and Mn powder in equal molar ratio into a ball milling tank, ball milling is carried out by adopting a wet method, a proper amount of absolute ethyl alcohol is poured, the ball-material ratio is 5:1, the rotating speed is 200-300 r/min, the ball milling time is 50-60 hours, and the mechanical alloying is stopped for half an hour every 4 hours; and then putting the ball-milled powder into a vacuum drying oven for drying, wherein the drying temperature is 70-90 ℃, the vacuum degree is-0.07 MPa-0.1 MPa, and the drying time is 8-12 hours.

Further, the raw material of the FeCoNiCrMn high-entropy alloy powder is in the TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following components in percentage by mass:

2.39-5.98% of Fe powder, 2.52-6.30% of Co powder, 2.51-6.28% of Ni powder, 2.23-5.56% of Cr powder and 2.35-5.88% of Mn powder.

Further, the TiB₂The purity of the powder is 99.5-99.9%, and the particle size is 2-5 microns.

Furthermore, the purity of the Fe powder, the purity of the Co powder, the purity of the Ni powder, the purity of the Cr powder and the purity of the Mn powder are 99.9-99.99%, and the particle size of the Cr powder and the Mn powder is 5-10 micrometers.

Further, the TiB₂Is powdered on the TiB₂The mass percentage of the-FeCoNiCrMn aluminum liquid corrosion resistant material is 80-88%.

Further, the raw material of the FeCoNiCrMn high-entropy alloy powder is in the TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following components in percentage by mass:

2.39-3.98% of Fe powder, 2.52-4.20% of Co powder, 2.51-4.19% of Ni powder, 2.23-3.71% of Cr powder and 2.35-3.92% of Mn powder.

Further, the TiB₂The densification degree of the FeCoNiCrMn molten aluminum corrosion resistant material is 94.1-98.6%, and the macro hardness is 51.24 HRC-74.36 HRC.

Further, the sintering adopts spark plasma sintering.

Further, the spark plasma sintering refers to: and (3) filling the dried powder into a mold, heating to the temperature T at the heating rate of 200-300 ℃, wherein the temperature T is 1400-1500 ℃, and preserving the heat for 5-10 minutes in the environment of the temperature T, and the pressure is 50-60 Mpa.

The preparation method comprises the following steps:

TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant materialThe preparation method of the material comprises the following steps:

step 1:

(1) mechanical alloying ball milling:

weighing Fe powder, Co powder, Ni powder, Cr powder and Mn powder with equal molar ratio, and putting the Fe powder, the Co powder, the Ni powder, the Cr powder and the Mn powder into a ball mill for ball milling to finally obtain single-phase FCC phase structure FeCoNiCrMn high-entropy alloy powder; in the FeCoNiCrMn high-entropy alloy powder, the components of Fe powder, Co powder, Ni powder, Cr powder and Mn powder in percentage by mass are as follows: 19.92% of Fe powder, 21.02% of Co powder, 20.93% of Ni powder, 18.54% of Cr powder and 19.59% of Mn powder. The mechanical alloying ball milling method is wet ball milling, wherein the ball milling process control agent is absolute ethyl alcohol, the ball-material ratio is 5:1, the rotating speed is 200-300 r/min, and the ball milling time is 50-60 hours; and stopping for half an hour every 4 hours.

(2) And (3) drying:

putting FeCoNiCrMn high-entropy alloy powder obtained by ball milling into a vacuum drying oven for drying; the drying temperature is 70-90 ℃, the preferred temperature is 90 ℃, the vacuum degree is-0.07 MPa-0.1 MPa, the preferred vacuum degree is-0.1 MPa, and the drying time is 8-12 hours, the preferred time is 12 hours.

Step 2:

(1) ball milling and powder mixing:

weighing TiB according to preset mass percentage₂Powder and FeCoNiCrMn high-entropy alloy powder are put into a ball mill for powder mixing; TiB₂The powder and the FeCoNiCrMn high-entropy alloy powder comprise the following components in percentage by mass: TiB₂70-88% of powder and 12-30% of FeCoNiCrMn high-entropy alloy powder, namely TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following components in percentage by mass of Fe powder, Co powder, Ni powder, Cr powder and Mn powder: 2.39-5.98% of Fe powder, 2.52-6.30% of Co powder, 2.51-6.28% of Ni powder, 2.23-5.56% of Cr powder and 2.35-5.88% of Mn powder. The powder mixing ball milling is wet ball milling, absolute ethyl alcohol is used as a ball milling medium, the ball-material ratio is 3:1, the rotating speed is 150-200 r/min, and the ball milling time is 2-4 hours.

(2) And (3) drying:

the TiB obtained after ball milling₂-FeCoNiCrMn mixed powder is put intoDrying in a vacuum drying oven; the drying temperature is 70-90 ℃, the preferred temperature is 90 ℃, the vacuum degree is-0.07 MPa-0.1 MPa, the preferred vacuum degree is-0.1 MPa, and the drying time is 8-12 hours, the preferred time is 12 hours.

And step 3:

sintering:

drying TiB₂And putting the FeCoNiCrMn mixed powder into a mould for spark plasma sintering. The sintering adopted by the invention is spark plasma sintering: and (3) filling the dried mixed powder into a mold, heating to the temperature T at the heating rate of 200-300 ℃/min, wherein the temperature T is 1400-1500 ℃, and preserving the heat for 5-10 minutes in the temperature T environment, and the pressure is 50-60 MPa.

The heating rate is 200 ℃/min, 250 ℃/min or 300 ℃/min; t is 1400 ℃ or 1500 ℃, and the holding time is 5, 6, 7, 8, 9 or 10 minutes.

Description of technical ideas of the present invention: TiB₂Has a plurality of excellent performances such as high hardness, high wear resistance, good high-temperature oxidation resistance and the like. But TiB₂Poor high-temperature toughness, low diffusion coefficient and poor sintering property, so that the pure TiB₂Sintering preparation of the material is difficult. Therefore, the characteristics of excellent toughness and low melting point of the metal binding phase can be utilized to improve TiB₂Poor toughness, difficult sintering and the like; while TiB₂The wettability with most metals is poor, so it is necessary to select one with TiB₂The metal with good wettability is used as a binding phase. In the experimental process, the FeCoNiCrMn high-entropy alloy is used as a binding phase, and a sintered sample has extremely high densification degree and the aluminum liquid corrosion resistance is greatly improved.

Has the advantages that: the invention discloses a TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material, the invention is characterized in that the material is prepared by adding TiB₂The ceramic powder is added with metal simple substance as a binding phase, thereby obviously reducing TiB₂The sintering temperature of the alloy improves TiB₂Sintering property of (2). And compared with the traditional sintering process, the spark plasma sintering process has great advantages, can obviously reduce the sintering temperature and the sintering time, and has the characteristics of low temperature, rapidness and high efficiency. Meanwhile, the inventionThe preparation process is simple, the price is low, the excellent corrosion resistance is shown in the aluminum liquid, and the method has important application value in industry.

TiB₂As the only stable compound of the transition group metal elements Ti and B, having a close-packed hexagonal C32 type crystal structure, TiB₂Meanwhile, the wear-resistant steel has strong Ti-B ionic bonds and B-B covalent bonds, so that the wear-resistant steel has high hardness, high wear resistance and good high-temperature oxidation resistance. But TiB₂Poor high-temperature toughness, low diffusion coefficient and poor sintering property, so that the pure TiB₂Sintering preparation of the material is difficult. Therefore, the characteristics of excellent toughness and low melting point of the metal binding phase can be utilized to improve TiB₂Poor toughness and difficult sintering. But TiB₂The wettability with most metals is poor, so that it is necessary to select a metal having good wettability with the metal as a binder phase. Therefore, a new metal system is designed as a binding phase, and a new sintering process is designed to improve TiB₂The material has the defect of difficult sintering, has excellent aluminum liquid corrosion resistance, low price of raw materials, simple preparation process and considerable industrial application prospect.

The application prospect is as follows: at present, the average corrosion rate of the cast iron material commonly used in the production industry in molten aluminum at 700 ℃ is 8.5 multiplied by 10^-1The average corrosion rate of mm/h, 316L stainless steel in aluminum liquid at 700 ℃ is 1.1 multiplied by 10^-1mm/h. In the first embodiment of the invention, the average corrosion rate of the material is 3.48 multiplied by 10^-4mm/h, compared with the common cast iron and 316L stainless steel in the current industrial production, the aluminum liquid corrosion resistance is greatly improved, and the test proves that TiB in the material₂The higher the content is, the better the corrosion resistance of the material is, and the material has good industrial application prospect.

Drawings

FIG. 1a is a microstructure diagram of a FeCoNiCrMn high entropy alloy powder in a first embodiment of the present invention;

FIG. 1b is an XRD pattern of a FeCoNiCrMn high entropy alloy powder in the first embodiment of the present invention;

FIG. 2a shows TiB in the first embodiment of the present invention₂-FeCoNiCrMn mixed powder after ball milling microscopicAn organizational chart;

FIG. 2b shows TiB in the first embodiment of the present invention₂-XRD pattern after ball milling of FeCoNiCrMn mixed powder;

FIG. 3 shows TiB prepared in the first embodiment of the present invention₂-a microstructure of a FeCoNiCrMn aluminium liquid corrosion resistant material;

FIG. 4 shows TiB prepared in the second embodiment of the present invention₂-a microstructure of a FeCoNiCrMn aluminium liquid corrosion resistant material;

FIG. 5 shows TiB prepared in the third embodiment of the present invention₂-a microstructure of a FeCoNiCrMn aluminium liquid corrosion resistant material;

FIG. 6 shows TiB prepared in example four of the present invention₂-a FeCoNiCrMn composite microstructure map;

FIG. 7 shows TiB at two sintering temperatures₂-FeCoNiCrMn aluminum liquid corrosion resistant material along with TiB₂Hardness profile of increased content;

FIG. 8 shows four embodiments of the invention, TiB₂-a time-varying graph of the corrosion depth of a FeCoNiCrMn aluminium liquid corrosion resistant material;

FIG. 9 shows TiB in the first embodiment of the present invention₂-microscopic structure picture of corrosion interface of FeCoNiCrMn aluminum liquid corrosion resistant material after aluminum liquid seed corrosion for 2, 5, 8, 10, 15 and 20 days at 700 ℃.

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 defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. 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.

The first embodiment is as follows: TiB₂The preparation method of the-FeCoNiCrMn aluminum liquid corrosion resistant material comprises the following steps:

(1) sample preparation: mixing TiB₂Fe, Co, Ni, Cr and Mn powder are weighed according to the following mass percent: TiB₂88 percent of powder and 2.39 percent of Fe powder2.52 percent of Co powder, 2.51 percent of Ni powder, 2.23 percent of Cr powder and 2.35 percent of Mn powder. The TiB₂The purity of the powder is 99.8%, and the particle size is 3 microns; the purity of the Fe powder, the Co powder, the Ni powder, the Cr powder and the Mn powder is 99.98 percent, and the granularity is 6 microns.

(2) Ball milling: mechanical alloying: putting Fe powder, Co powder, Ni powder, Cr powder and Mn powder in a molar ratio into a ball milling tank, performing wet ball milling, pouring a proper amount of absolute ethyl alcohol, performing ball milling for 60 hours at a ball-material ratio of 5:1, keeping the ball milling at the rotating speed of 300r/min for half an hour every 4 hours, and then drying the ball milling tank in a vacuum drying oven for 12 hours at the drying temperature of 90 ℃ and the vacuum degree of below-0.1 MPa to finally obtain the FeCoNiCrMn high-entropy alloy powder with the single FCC phase structure. FIG. 1a is a microstructure diagram of FeCoNiCrMn high-entropy alloy powder, and it can be seen from FIG. 1a that FeCoNiCrMn high-entropy alloy powder with uniform size is obtained. FIG. 1b is an XRD pattern of FeCoNiCrMn high entropy alloy powder in this example, and it can be seen that a single FCC structure has been formed.

② FeCoNiCrMn high-entropy alloy powder and TiB obtained by the steps₂The powder is prepared according to the preset mass ratio (88% TiB)₂Powder, 12% FeCoNiCrMn high entropy alloy powder) is put into a ball milling tank, and the required balls are weighed and put into the ball milling tank according to the ball to mixture mass ratio of 3: 1. And (3) adopting a wet ball milling process, and pouring a proper amount of absolute ethyl alcohol into the ball milling tank to cover the powder. The rotating speed of the ball mill is 200r/min, and the ball milling time is 4 hours.

(3) And (3) drying: ball-milled TiB₂The FeCoNiCrMn mixed powder is put into a vacuum drying oven for drying, the temperature of the drying oven is 90 ℃, the vacuum degree is-0.1 MPa, and the drying time is 12 hours. The dried powder was taken out for further use. FIG. 2(a) is TiB₂SEM image of mixed powder of FeCoNiCrMn after ball milling. It can be seen from the figure that after the ball milling and powder mixing, the high-entropy alloy powder is uniformly dispersed in TiB₂In the powder, the powder mixing effect is better. FIG. 2 (b) is TiB₂XRD pattern of the mixed powder of-FeCoNiCrMn after ball milling, it can be seen that, in addition to TiB₂Besides the diffraction peak, the diffraction peak of FeCoNiCrMn high-entropy alloy can be observed.

(4) And (3) sintering: this exampleThe sintering equipment used is spark plasma sintering, the dried powder obtained in the previous step is placed into a cylindrical graphite die and then placed into sintering equipment for sintering, and the sintering process is set as follows: the temperature is raised from room temperature to 1500 ℃ at the heating rate of 300 ℃/min, the temperature is kept at 1500 ℃ for 7 minutes, and the pressure is increased by 50-60 MPa in the sintering process. Cooling along with the furnace after sintering is finished, and then demoulding to obtain TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material sample. FIG. 3 shows TiB obtained in this example₂-microstructure of a sample of FeCoNiCrMn aluminium liquid corrosion resistant material under Scanning Electron Microscope (SEM). From the SEM image, it can be seen that the dark gray is TiB₂Hard phase, light gray and bright is high-entropy alloy binding phase which is distributed in TiB₂Around the hard phase, TiB is filled₂The surrounding void.

Compared with the traditional sintering process (pressureless sintering, hot-pressing sintering and the like), the Spark Plasma Sintering (SPS) has the following advantages: the method has the characteristics of high heating rate, low sintering temperature, short sintering time and the like, can prepare high-density materials at a lower temperature, is commonly used for preparing ceramic materials difficult to sinter, generates discharge plasma when the electrode is introduced with direct-current pulse current in the sintering process, purifies the surfaces of particles, and enables each particle to uniformly generate Joule heat per se and activate the surfaces of the particles. Therefore, the sintering can be completed quickly and efficiently, the energy is saved, the production cost is reduced, and the production efficiency is improved.

The spark plasma sintering can be carried out by FAS-10015Y spark plasma sintering equipment or other equipment manufactured by Shanghai Kangshi electric furnace equipment Co.

(5) Aluminum liquid corrosion resistance test: the sintered cake-shaped TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material sample (size is) Cutting into 5 × 5 × 8mm cuboid sample with a spark numerical control wire cutting machine, placing the cuboid sample into a graphite crucible filled with 700 deg.C aluminum liquid for corrosion experiment, heating and maintaining with a well-type resistance furnace, and dividing into two partsTaking out after 2 days, 5 days, 8 days, 10 days, 15 days and 20 days of corrosion.

Calculating TiB₂The corrosion depth and the corrosion rate of the FeCoNiCrMn molten aluminum corrosion-resistant material sample at different time are measured by a depth method in the experiment, and the calculation formula is as follows: v ═ a-b)/2 t.

Wherein a is TiB₂-thickness of FeCoNiCrMn aluminum liquid corrosion resistant material sample before corrosion, and b is TiB₂-thickness of FeCoNiCrMn aluminum liquid corrosion resistant material sample after corrosion, t is corrosion time, thickness a before corrosion is accurately measured by a micrometer before corrosion experiment, and then TiB is subjected to scanning electron microscope₂Observing the structure of the cross section of the FeCoNiCrMn aluminum liquid corrosion resistant material sample after corrosion, and measuring TiB by using Smile View software₂The residual thickness b of the FeCoNiCrMn aluminum liquid corrosion resistant material sample after corrosion.

Calculating the TiB obtained in this example₂The corrosion rate of a sample of the aluminum liquid corrosion resistant material of FeCoNiCrMn is 3.48 multiplied by 10^-4mm/h. TiB obtained in this example was tested using a Rockwell hardness tester type HR-150A₂The macro hardness of the-FeCoNiCrMn aluminum liquid corrosion resistant material sample is 74.36 HRC.

Example two: compared with the method in the first embodiment, the method in the second embodiment is the same except that the step (4) is different; step (4) sintering of example 2: the sintering equipment used in this example was spark plasma sintering, and the dried powder was placed in a cylindrical graphite mold and then sintered in the sintering equipment, and the sintering process was set as follows: heating from room temperature to 1400 ℃ at a heating rate of 300 ℃/min, preserving heat at 1400 ℃ for 7 minutes, and pressurizing at 50-60 MPa in the sintering process. Cooling along with the furnace after sintering is finished, and then demoulding to obtain TiB₂-FeCoNiCrMn aluminum liquid corrosion resistant material sample. Calculate TiB obtained in this example₂The corrosion rate of the-FeCoNiCrMn molten aluminum corrosion resistant material is 5.79 multiplied by 10^-4mm/h. TiB obtained in this example was tested using a Rockwell hardness tester type HR-150A₂The macroscopic hardness of the FeCoNiCrMn molten aluminum corrosion-resistant material is 69.32 HRC.

FIG. 4 shows TiB obtained in this example₂-FeCoNiCrMn aluminum liquid corrosion resistant materialAnd (3) a microscopic morphology SEM tissue picture of the material sample. This example TiB₂FIG. 8 shows the relationship between the corrosion depth of the FeCoNiCrMn molten aluminum corrosion-resistant material and the time.

Example three: compared with the second embodiment, the method of the third embodiment is the same as that of the second embodiment except that the step (1) is different; step (1) of example three, sample preparation: mixing TiB₂Fe, Co, Ni, Cr and Mn powder are weighed according to the following mass percent: TiB₂80% of powder, 3.98% of Fe powder, 4.20% of Co powder, 4.19% of Ni powder, 3.71% of Cr powder and 3.92% of Mn powder. The TiB₂The purity of the powder is 99.5%, and the particle size is 5 microns; the purity of the Fe powder, the Co powder, the Ni powder, the Cr powder and the Mn powder is 99.9 percent, and the granularity is 10 microns. The other steps are the same as in the example. Calculate TiB obtained in this example₂The corrosion rate of the-FeCoNiCrMn molten aluminum corrosion resistant material is 5.70 multiplied by 10^-3mm/h. TiB obtained in this example was tested using a Rockwell hardness tester type HR-150A₂The macroscopic hardness of the FeCoNiCrMn molten aluminum corrosion-resistant material is 54.61 HRC.

FIG. 5 shows TiB of this example₂-microscopic appearance SEM organizational chart of sintered FeCoNiCrMn aluminum liquid corrosion resistant material sample. The erosion depth of this material as a function of time is shown in FIG. 8.

Example four: compared with the first embodiment, the method of the fourth embodiment is the same except that the step (1) is different; step (1) of example four sample preparation: mixing TiB₂Fe, Co, Ni, Cr and Mn powder are weighed according to the following mass percent: TiB₂70% of powder, 5.98% of Fe powder, 6.30% of Co powder, 6.28% of Ni powder, 5.56% of Cr powder and 5.88% of Mn powder. The TiB₂The purity of the powder is 99.5%, and the particle size is 5 microns; the purity of the Fe powder, the Co powder, the Ni powder, the Cr powder and the Mn powder is 99.9 percent, and the granularity is 10 microns. The other steps are the same as in the first embodiment. Calculating the TiB obtained in this example₂The corrosion rate of the-FeCoNiCrMn molten aluminum corrosion resistant material is 6.31 multiplied by 10^-3mm/h. TiB obtained in this example was tested using a Rockwell hardness tester type HR-150A₂The macroscopic hardness of the FeCoNiCrMn molten aluminum corrosion resistant material is 51.24 HRC.

FIG. 6 shows TiB of this example₂-FeCoNiCrMn aluminum liquid corrosion resistant materialAnd (3) SEM (scanning electron microscope) tissue diagram of the sintered micro-morphology of the material sample. The erosion depth of this material as a function of time is shown in FIG. 8.

FIG. 8 shows four TiB types in the first, second, third and fourth embodiments₂-FeCoNiCrMn aluminum liquid corrosion resistant material corrosion depth time-dependent curve chart. As can be seen from the figure, the TiB of the same species increased with the etching time₂Powder content of TiB₂the-FeCoNiCrMn aluminum liquid corrosion resistant material sample has high sintering temperature and good aluminum liquid corrosion resistance, and 88 percent of TiB at the same sintering temperature₂TiB of powder₂The sample ratio of the-FeCoNiCrMn molten aluminum corrosion resistant material to the TiB is 80 percent₂Powder and 70% TiB₂TiB of powder₂The FeCoNiCrMn aluminum liquid corrosion resistant material sample has good aluminum liquid corrosion resistance, and the corrosion rate is reduced along with the extension of time. Calculation of TiB obtained in example one₂The average corrosion rate of the FeCoNiCrMn aluminum liquid corrosion resistant material is as follows: 3.48X 10^-4mm/h; TiB obtained in example II₂The average corrosion rate of the FeCoNiCrMn aluminum liquid corrosion resistant material is as follows: 5.79X 10^-4mm/h; TiB obtained in example III₂The average corrosion rate of the FeCoNiCrMn aluminum liquid corrosion resistant material is as follows: 5.70X 10^-3mm/h; TiB obtained in example four₂The average corrosion rate of the FeCoNiCrMn aluminum liquid corrosion resistant material is as follows: 6.31X 10^-3mm/h. Compared with the corrosion rate of cast iron in molten aluminum of 0.85mm/h, TiB in the embodiment₂The aluminum liquid corrosion resistant rate of the FeCoNiCrMn aluminum liquid corrosion resistant material is greatly improved.

FIG. 9 shows TiB obtained in example I₂Microstructure of the corrosion interface of the FeCoNiCrMn aluminum liquid corrosion resistant material after 2, 5, 8, 10, 15, 20 days of corrosion in aluminum liquid at 700 ℃ (corresponding to fig. 9(a) - (f), respectively). In the experiment, the aluminum liquid pair TiB is found₂the-FeCoNiCrMn aluminum liquid corrosion resistant material generates corrosion, but the corrosion layer does not separate from the matrix and is dissociated in the aluminum liquid, and TiB₂The FeCoNiCrMn aluminum liquid corrosion resistant material still keeps the original shape, provides a practical and reliable preparation technology for the preparation of aluminum liquid corrosion resistant composite materials, and has higher practical significance.

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.