阅读说明：本技术 一种耐熔融铝腐蚀的金属陶瓷复合材料的制备方法 (Preparation method of metal ceramic composite material resistant to molten aluminum corrosion ) 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的制备方法,步骤1：物料准备；准备MoSi<Sub>2</Sub>粉和钴粉,其中MoSi<Sub>2</Sub>粉的质量百分百为85-90％,余量为钴粉；步骤2：球磨混粉；将MoSi<Sub>2</Sub>粉和钴粉置于球磨罐进行球磨；球磨后的混合物进行干燥处理；步骤3：烧结；将干燥处理后的混合物进行烧结,烧结温度为1200℃-1250℃。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 preparation method of a metal ceramic composite material resistant to molten aluminum corrosion, which comprises the following steps of 1: preparing materials; preparation of MoSi 2 Powder and cobalt powder, in which MoSi 2 85-90% of powder by mass percent, and the balance being cobalt powder; step 2: ball milling and mixing powder; mixing MoSi 2 Placing the powder and cobalt powder in a ball milling tank for ball milling; drying the mixture after ball milling; and step 3: sintering; sintering the dried mixture at 1200-1250 ℃. The molten aluminum corrosion resistant MoSi provided by the invention 2 -Co cermet compositeMoSi used in the material 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. A preparation method of a metal ceramic composite material resistant to corrosion of molten aluminum is characterized by comprising the following steps:

step 1: preparing materials;

preparation of MoSi ₂Powder and cobalt powder, in which MoSi ₂85-90% of powder by mass percent, and the balance being cobalt powder;

step 2: ball milling and mixing powder;

mixing MoSi ₂Placing the powder and cobalt powder in a ball milling tank for ball milling; drying the mixture after ball milling;

and step 3: sintering;

sintering the dried mixture at 1200-1250 ℃.

2. The method of claim 1, wherein MoSi is used to prepare the cermet composite material with resistance to corrosion from molten aluminum ₂The purity of the powder is 99.9 percent, the purity of the cobalt powder is 99.9 percent, and the granularity is 1-2 microns.

3. The method for preparing the metal ceramic composite material resistant to corrosion of molten aluminum according to claim 1, wherein in the ball milling and mixing, the ball-to-material ratio is between 3: 1 and 10: 1, the rotating speed is between 180r/min and 220r/min, and the ball milling time is between 2h and 5 h.

4. The method for preparing the molten aluminum corrosion resistant cermet composite material of claim 1 wherein the drying step is drying the ball milling jar in a vacuum drying oven for 7-9 hours at 80-100 ℃ after the ball milling.

5. The method of claim 1, wherein the dry powder is cooled and then ground in a mortar to reduce the hardening of the powder, and the particle size of the ground powder is in the range of 1-2 μm.

6. The method of claim 1, wherein sintering is spark plasma sintering.

7. The method for preparing the molten aluminum corrosion resistant cermet composite material of claim 6 wherein the pressure value applied during spark plasma sintering is 20-40MPa and the holding time is 3-10 min.

8. The method of claim 1, wherein MoSi is used to prepare the cermet composite material with resistance to corrosion from molten aluminum ₂The content of the powder is 85%, 88% or 90%.

9. The method of making a fused aluminum corrosion resistant cermet composite as claimed in any one of claims 1 to 8 wherein the cermet composite is MoSi ₂-Co cermet composite material, said MoSi ₂-12Co cermet composite material having a 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。

Technical Field

The invention belongs to the field of molten aluminum corrosion resistant materials, and particularly relates to a preparation method of 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, Ni ₃Al, 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 Al ₂O ₃Etc. are widely used for aluminumBut the ceramic is brittle and difficult to process. The metal ceramic has the performance between that of ceramic and metal, has good mechanical performance and corrosion resistance, and MoSi ₂The metal ceramic is a high-temperature oxidation resistant metal ceramic, has good aluminum liquid corrosion resistance, but has little attention in 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 a preparation method of the metal ceramic composite material with molten aluminum corrosion resistance, and the preparation method of the metal ceramic composite material with molten aluminum corrosion resistance has the advantages of low cost, easy preparation and obvious molten aluminum corrosion resistance.

The technical solution of the invention is as follows:

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

step 1: preparing materials;

preparation of MoSi ₂Powder and cobalt powder, in which MoSi ₂85-90% of powder by mass percent, and the balance being cobalt powder;

step 2: ball milling and mixing powder;

mixing MoSi ₂Placing the powder and cobalt powder in a ball milling tank for ball milling; drying the mixture after ball milling;

and step 3: sintering;

sintering the dried mixture at 1200-1250 ℃.

MoSi ₂The purity of the powder is 99.9 percent, the purity of the cobalt powder is 99.9 percent, and the granularity is 1-2 microns.

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

The drying step is that the ball milling tank is placed in a vacuum drying oven for drying for 7-9h after the ball milling is finished, and the drying temperature is 80-100 ℃. Preferably 8 hours and 90 ℃.

And after the dried powder is cooled, grinding the powder by using a mortar to reduce the hardening of the powder, wherein the grain diameter of the ground powder is 1-2 microns.

Sintering refers to sintering by spark plasma.

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

MoSi ₂The content of the powder is 85%, 88% or 90%.

The metal ceramic composite material is MoSi ₂-Co cermet composite material, said MoSi ₂-12Co cermet composite material having a 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。

Description of technical route:

MoSi with higher performance through aluminum corrosion resistance ₂The 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 sintering ₂Co reacts to generate a CoMoSi ternary phase, and the CoMoSi ternary phase belongs to laves phases, so that MoSi is generated ₂The 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 preparation method of a metal ceramic composite material resisting molten aluminum corrosion, wherein the material is MoSi ₂-Co cermet composite material, said MoSi ₂-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 MoSi ₂MoSi for use in-Co cermet composites ₂Low cost and high Co contentThe preparation method has the advantages of low cost, simple preparation and good application prospect in the aluminum corrosion resistant industry.

Drawings

FIG. 1 is 88% MoSi ₂-XRD pattern after sintering of 12% Co cermet composite.

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

FIG. 3 is 88% MoSi ₂SEM image of interface structure after 1 day corrosion of-12% Co in 700 ℃ aluminum liquid.

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

FIG. 5 is 88% MoSi ₂SEM image of interface structure of-12% Co after 3 days of corrosion in 700 ℃ aluminum liquid.

FIG. 6 is 88% MoSi ₂SEM image of interface structure of-12% Co after 4 days of corrosion in 700 ℃ aluminum liquid.

FIG. 7 is 88% MoSi ₂SEM 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 sintering ₂Texture map of 10% Co cermet composite.

FIG. 10 is the 85% MoSi after sintering ₂-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 MoSi ₂Powder and cobalt powder are used as raw materials. Wherein, MoSi ₂The purity of the cobalt is 99.9 percent, and the particle sizes are all 1-2 microns.

(2) Ball milling mixed powder

Weighing pure MoSi ₂Pouring the powder and cobalt powder into a 250ml hard alloy tank, adding hard alloy balls with the diameter of 2-5mm (the average diameter of the alloy balls in the hard alloy tank is the same, and the diameter is 2-5mm, such as 2mm or 5mm) according to the ball material ratio of 3: 1 to 10: 1, and then pouring a proper amount of alcohol for wet mixing, wherein the alcohol is just submerged in 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.