阅读说明：本技术 一种耐熔融铝腐蚀的金属陶瓷复合材料 (Metal ceramic composite material resistant to corrosion of molten aluminum ) 是由 尹付成 易华清 王鑫铭 欧阳雪枚 尚岩松 谢小龙 刘克 于 2019-11-29 设计创作，主要内容包括：本发明公开了一种耐熔融铝腐蚀的金属陶瓷复合材料,金属陶瓷复合材料为MoSi<Sub>2</Sub>-Co金属陶瓷复合材料,MoSi<Sub>2</Sub>-Co金属陶瓷复合材料由如下按质量百分比计的组分构成：MoSi<Sub>2</Sub>85-90％,余量为Co；所述MoSi<Sub>2</Sub>-12Co金属陶瓷复合材料在700℃熔融铝中的腐蚀速率为4.10微米/小时～7.10微米/小时,显微硬度为839.2HV<Sub>0.2</Sub>～1384.1HM<Sub>0.2</Sub>。本发明提供的耐熔融铝腐蚀的MoSi<Sub>2</Sub>-Co金属陶瓷复合材料中所用的MoSi<Sub>2</Sub>价格便宜,钴的含量较少成本较低,制备较为简单,在耐铝腐蚀工业中具有良好的应用前景。(The invention discloses a metal ceramic composite material resisting corrosion of molten aluminum, which is MoSi 2 -Co cermet composite, MoSi 2 the-Co metal ceramic composite material comprises the following components in percentage by mass: MoSi 2 85-90% and the balance of Co; the MoSi is 2 The corrosion rate of the-12 Co metal ceramic composite material in molten aluminum at 700 ℃ is 4.10-7.10 microns/hour, and the microhardness is 839.2HV 0.2 ～1384.1HM 0.2 . The molten aluminum corrosion resistant MoSi provided by the invention 2 MoSi for use in-Co cermet composites 2 The cobalt-based composite material has the advantages of low price, low cobalt content, low cost, simple preparation and good application prospect in the aluminum corrosion resistance industry.)

1. The metal ceramic composite material resisting molten aluminum corrosion is characterized in that the metal ceramic composite material is MoSi₂-Co cermet composite, MoSi₂the-Co metal ceramic composite material comprises the following components in percentage by mass:

MoSi₂85-90% and the balance of Co;

the MoSi is₂The corrosion rate of the-12 Co metal ceramic composite material in molten aluminum at 700 ℃ is 4.10-7.10 microns/hour, and the microhardness is 839.2HV_0.2～1384.1HV_0.2。

2. The fused aluminum corrosion resistant cermet composite of claim 1, in which commercially pure MoSi is used₂Powder and cobalt powder as raw materials, MoSi₂The purity of the powder was 99.9%, and the purity of the cobalt powder was 99.9%.

3. The fused aluminum corrosion resistant cermet composite of claim 1, wherein the MoSi is characterized by₂The content of the powder is 85%, 88% or 90%.

4. The fused aluminum corrosion resistant cermet composite of any of claims 1-3, wherein MoSi₂-Co cermet composite material via MoSi₂The powder and cobalt powder are mixed by ball milling and sintered by discharge plasma.

5. The fused aluminum corrosion resistant cermet composite material of claim 4 wherein the ball-milling mixing is performed at a ball-to-material ratio of 3: 1 to 10: 1, a rotational speed of 180r/min to 220r/min, and a ball-milling time of 2h to 5 h.

6. The fused aluminum corrosion resistant cermet composite material of claim 4, wherein the ball milling jar is placed in a vacuum drying oven for drying for 7-9 hours after ball milling, and the drying temperature is 80-100 ℃.

7. The molten aluminum corrosion-resistant metal ceramic composite material as claimed in claim 4, wherein the dry powder is cooled and then ground by a mortar to reduce the hardening of the powder, and the particle size of the ground powder is 1-2 μm.

8. The fused aluminum corrosion resistant cermet composite of claim 4, wherein the sintering temperature during spark plasma sintering is 1200-1250 ℃.

9. The fused aluminum corrosion resistant cermet composite material of claim 8, wherein the pressure value applied during spark plasma sintering is 20-40 MPa, and the holding time is 3-10 min.

Technical Field

The invention belongs to the field of molten aluminum corrosion resistant materials, and particularly relates to a molten aluminum corrosion resistant metal ceramic composite material.

Background

In modern industries, corrosion caused by molten metal is quite common due to the need to transport and handle the molten metal. In the production of melting, forming (casting) and hot dip aluminizing in the aluminum industry, parts such as crucibles, molds, fixtures and the like are severely corroded, and problems such as perforation of a melting container, adhesion of the surface of a metal mold and the like are caused. Therefore, failure due to severe corrosion of the crucible and mold by molten aluminum is inevitable in the aluminum industry.

Aiming at aluminum liquid corrosion, a plurality of materials with aluminum liquid corrosion resistance are explored in the industry. Iron-based materials are the most used materials for molds and crucibles in the aluminum industry, and thus much research has been conducted on their corrosion resistance in molten aluminum. The iron-based material cannot effectively resist the strong corrosion and abrasion of aluminum in the aluminum industry at present, so that the equipment is frequently replaced and the production efficiency is reduced. In the aspect of refractory metals, compared with iron-based materials, the reaction between cobalt-based materials and liquid aluminum is more uniform and mild, but the cobalt-based materials are expensive. In the Mo-W system, the Nb-based alloy has good aluminum liquid corrosion resistance, but the hardness is higher, and the processing difficulty is high, so that the large-scale application of the Mo-W system and the Nb-based alloy is limited. In recent years, high-entropy alloy has a certain development in aluminum liquid corrosion resistance, but the aluminum liquid corrosion resistance of the existing mature AlFeNiCoCr high-entropy alloy is not good. Intermetallic compounds are a unique class of materials, Ni₃Al, NiAl, FeSi and the like have good corrosion resistance in molten aluminum, but the production process of intermetallic compounds is complex and the cost is high. Ceramics possess excellent resistance to molten aluminum corrosion, like graphite, AlN, and Al₂O₃And the like are widely used for smelting aluminum, but ceramics have high brittleness and are difficult to process. The metal ceramic has the performance between that of ceramic and metal, has good mechanical performance and corrosion resistance, and MoSi₂Is a metal ceramic with high temperature oxidation resistance and high temperature oxidation resistanceThe aluminum liquid corrosion performance is good, but the attention is paid to the aluminum liquid corrosion resistance.

Therefore, there is a need for a new method for preparing a cermet composite material that is resistant to corrosion by molten aluminum.

Disclosure of Invention

The technical problem to be solved by the invention is to provide the metal ceramic composite material with molten aluminum corrosion resistance, which has the advantages of low cost, easy preparation and obvious molten aluminum corrosion resistance.

The technical solution of the invention is as follows:

a metal ceramic composite material resisting corrosion of molten aluminum, wherein the metal ceramic composite material is MoSi₂-Co cermet composite, MoSi₂the-Co metal ceramic composite material comprises the following components in percentage by mass:

MoSi₂85-90% and the balance of Co;

the MoSi is₂The corrosion rate of the-12 Co metal ceramic composite material in molten aluminum at 700 ℃ is 4.10-7.10 microns/hour, and the microhardness is 839.2HV_0.2～1384.1HV_0.2。

Adopts industrial pure MoSi₂Powder and cobalt powder as raw materials, MoSi₂The purity of the powder is 99.9 percent, the purity of the cobalt powder is 99.9 percent, and the purity is percent by mass.

MoSi₂The content of the powder is 85%, 88% or 90%.

MoSi₂-Co cermet composite material via MoSi₂The powder and cobalt powder are mixed by ball milling and sintered by discharge plasma.

In ball milling and mixing, the ball-material ratio is between 3: 1 and 10: 1, the rotating speed is between 180r/min and 220r/min, the ball milling time is 2h to 5h, and the ball-material ratio is the mass ratio.

And after ball milling, placing the ball milling tank in a vacuum drying oven for drying for 7-9 h, wherein the drying temperature is 80-100 ℃. Preferably 8 hours and 90 ℃.

And after the dry powder is cooled, grinding the powder by using a mortar to reduce the hardening of the powder, wherein the grain size of the ground powder ranges from 1 micron to 2 microns.

In the discharge plasma sintering process, the sintering temperature is 1200-1250 ℃.

In the discharge plasma sintering process, the applied pressure value is 20-40 MPa, the heat preservation time is 3-10 min, the preferred pressure value is 30MPa, and the heat preservation time is 5 min.

Description of technical route:

MoSi with higher performance through aluminum corrosion resistance₂The metal ceramic realizes the molten aluminum corrosion resistance, and simultaneously, in order to improve the mechanical property of the sintered ceramic, a certain amount of cobalt is added to improve the plasticity and toughness of the sintered ceramic. MoSi was found after sintering₂Co reacts to generate a CoMoSi ternary phase, and the CoMoSi ternary phase belongs to laves phases, so that MoSi is generated₂The corrosion resistance of the-Co metal ceramic composite material is more excellent. As the sintering process of the cermet which is widely used in the current practical industrial application and is 90 percent WC-10 percent Co, 88 percent WC-12 percent Co and 85 percent WC-15 percent Co is mature, a similar sintering process is selected, and the component proportion selected in the embodiment is made according to a Co-Mo-Si ternary phase diagram.

Has the advantages that:

the invention discloses a metal ceramic composite material resisting corrosion of molten aluminum, which is MoSi₂-Co cermet composite material, said MoSi₂-Co cermet composite material having corrosion rate of 4.10 to 7.10 microns per hour in 700 ℃ molten aluminum and microhardness of 839.2HV_0.2-1384.1HV_0.2. The embodiment of the invention provides molten aluminum corrosion resistant MoSi₂MoSi for use in-Co cermet composites₂The cobalt-based composite material has the advantages of low price, low cobalt content, low cost, simple preparation and good application prospect in the aluminum corrosion resistance industry.

Drawings

FIG. 1 is 88% MoSi₂-XRD pattern after sintering of 12% Co cermet composite.

FIG. 2 shows MoSi after sintering₂-12Co cermet composite texture map.

FIG. 3 is 88% MoSi₂Interface group of-12% Co corroded in aluminum liquid at 700 ℃ for 1 daySEM image.

FIG. 4 is 88% MoSi₂SEM image of interface structure of-12% Co after 2 days of corrosion in aluminum liquid at 700 ℃.

FIG. 5 is 88% MoSi₂SEM image of interface structure of-12% Co after 3 days of corrosion in 700 ℃ aluminum liquid.

FIG. 6 is 88% MoSi₂SEM image of interface structure of-12% Co after 4 days of corrosion in 700 ℃ aluminum liquid.

FIG. 7 is 88% MoSi₂SEM image of interface structure of-12% Co after 5 days of corrosion in 700 ℃ aluminum liquid.

FIG. 8 is a graph showing the corrosion kinetics of three examples in a 700 ℃ aluminum liquid.

FIG. 9 is the 90% MoSi after sintering₂Texture map of 10% Co cermet composite.

FIG. 10 is the 85% MoSi after sintering₂-texture map of 15% Co cermet composite.

Detailed Description

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

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

The preparation method of the metal ceramic composite material resisting molten aluminum corrosion comprises the following steps:

(1) material preparation

Adopts industrial pure MoSi₂Powder and cobalt powder are used as raw materials. Wherein, MoSi₂The purity of the cobalt is 99.9 percent, and the particle sizes are all 1-2 microns.

(2) Ball milling mixed powder

Weighing pure MoSi₂Pouring the powder and cobalt powder into a 250ml cemented carbide tank, and placing cemented carbide balls (mean diameter phase of the cemented carbide balls in the cemented carbide tank) with diameter of 2-5mm according to the ball-to-material ratio of 3: 1 to 10: 1The diameter is 2-5mm, such as 2mm or 5mm), and adding appropriate amount of alcohol for wet mixing, wherein the alcohol should just submerge the powder; after the steps are completed, sealing the tank body and filling argon into the tank body so as to avoid the oxidation of the materials in the powder mixing process; after the powder is filled, filling the ball mill tank into a ball mill and setting a program, wherein the rotating speed is between 180r/min and 220r/min, and the time is 2-5 h; after ball milling, the ball milling tank is placed in a vacuum drying oven for drying for 8 hours, the drying temperature is 90 degrees, the heating rate is 3 degrees, and the vacuum degree is 1.0 multiplied by 10^-3MPaMPa; and after the powder is cooled, grinding the powder by using a mortar to reduce the hardening of the powder, and finally obtaining the powder before sintering, wherein the particle size of the powder is 1-2 microns.

(3) Spark plasma sintering

The pre-powder was placed in a cylindrical graphite mold with a diameter of 40mm and a length of 100 mm. The hot-pressing sintering temperature is 1200-1250 ℃, the applied pressure value is 30MPa, the heat preservation time is 5min, and after the sintering is finished, the sample is taken out after the temperature is cooled to the room temperature.