阅读说明：本技术 一种超细晶定向分布钼镍硼金属陶瓷材料及其制备方法 (Ultrafine grain oriented molybdenum-nickel-boron cermet material and preparation method thereof ) 是由 李文虎 艾桃桃 董洪峰 卫学玲 邹祥宇 寇领江 冯小明 于 2021-06-17 设计创作，主要内容包括：本发明公开了一种超细晶定向分布钼镍硼金属陶瓷材料及其制备方法,包括：将钼箔、镍箔与镍硼箔表面进行粗化处理；对镍箔、钼箔、镍硼箔进行双面活化,清洗；累计叠轧,控制轧辊转速、轧制温度,累计叠轧若干层；将叠轧成型的金属陶瓷进行无压热处理,降温,得到具有超细晶粒与组织定向分布的金属陶瓷材料。该方法工艺简单,制得的钼镍硼金属陶瓷具有超细晶粒与组织的定向分布以及良好的力学性能。(The invention discloses a molybdenum-nickel-boron cermet material with ultra-fine grain oriented distribution and a preparation method thereof, wherein the preparation method comprises the following steps: roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil; activating the two sides of the nickel foil, the molybdenum foil and the nickel boron foil, and cleaning; accumulating and rolling, controlling the rotating speed and the rolling temperature of the roller, and accumulating and rolling a plurality of layers; and carrying out non-pressure heat treatment on the metal ceramic formed by the pack rolling, and cooling to obtain the metal ceramic material with ultra-fine grains and directionally distributed structures. The method has simple process, and the prepared molybdenum-nickel-boron cermet has directional distribution of ultrafine grains and structures and good mechanical properties.)

1. A preparation method of a molybdenum-nickel-boron cermet material with ultra-fine grain oriented distribution is characterized by comprising the following steps:

1) roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil;

2) activating the two sides of the nickel-boron foil and the nickel foil, and then cleaning;

3) sequentially and cumulatively rolling the nickel foil, the molybdenum foil, the nickel-boron foil, the nickel foil, the molybdenum foil, the nickel-boron foil … …, the nickel foil, the molybdenum foil, the nickel-boron foil and the nickel foil in sequence, controlling the rotating speed and the rolling temperature of the roller, and cumulatively rolling for 30-80 layers;

4) and carrying out non-pressure heat treatment on the metal ceramic formed by the stack rolling, controlling the heat treatment temperature and the vacuum degree, and cooling after the non-pressure heat treatment to obtain the metal ceramic material with ultra-fine grains and directionally distributed structures.

2. The method for preparing an ultra-fine grain-oriented molybdenum-nickel-boron cermet material according to claim 1, wherein the purities of the molybdenum foil, the nickel-boron foil and the nickel foil are not less than 99.9%, the thicknesses of the molybdenum foil and the nickel-boron foil are not more than 0.1mm, and the thickness of the nickel foil is 1 mm.

3. The method for preparing the molybdenum-nickel-boron cermet material with ultra-fine grain-oriented distribution as claimed in claim 1, wherein the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil are roughened, and the ratio Ra of the molybdenum foil, the nickel foil and the nickel-boron foil is controlled to be 0.1 μm and less than 1.0 μm.

4. The method for preparing the ultra-fine grain oriented molybdenum-nickel-boron cermet material according to claim 1, wherein hydrochloric acid and nitric acid solutions with a mass ratio of 2:1 are used for double-sided activation of the molybdenum foil, concentrated hydrochloric acid and concentrated nitric acid solutions with a mass ratio of 3:1 are used for double-sided coating activation of the nickel-boron foil and the nickel foil, and then absolute ethyl alcohol is used for cleaning.

5. The method for preparing the ultra-fine grain oriented molybdenum-nickel-boron cermet material according to claim 1, wherein the rolling process comprises: the rotating speed of the roller is 0.1-0.5 m/min, and the rolling temperature is 850-950 ℃.

6. The method for preparing the ultra-fine grain oriented molybdenum-nickel-boron cermet material of claim 1, wherein the pack-rolled cermet is subjected to pressureless heat treatment in a vacuum heat treatment furnace.

7. The method for preparing Mo-Ni-B cermet material with ultra-fine grain oriented distribution as claimed in claim 6, wherein the heating rate of the heat treatment is 5-10 ℃/min, the temperature is increased to 600-800 ℃, and the degree of vacuum is less than or equal to 10^-2Pa; the cooling speed is 3-10 ℃/min, and the temperature is reduced to the room temperature.

8. The method for preparing Mo-Ni-B cermet materials with ultra-fine grain oriented distribution as claimed in claim 1, wherein the Mo-Ni-B cermet materials obtained has a maximum degree of compaction up to 99.1%, a maximum bending strength of not less than 1970MPa, and a maximum fracture toughness of not less than 28.6 MPa-m^1/2The highest hardness is not lower than HRA85, and the oxidation resistance is completely realized at 800-1000 ℃.

9. An ultra-fine grain oriented molybdenum nickel boron cermet material prepared by the method of any one of claims 1-8.

Technical Field

The invention relates to the preparation of metal ceramics, in particular to a molybdenum-nickel-boron metal ceramic material with ultra-fine grain oriented distribution and a preparation method thereof.

Background

The molybdenum-nickel-boron cermet is an important ceramic material in modern industry, and the development of the cermet plays a significant role in the development of the industrial fields of aerospace, aviation, energy power and the like.

The molybdenum-nickel-boron cermet mainly comprises a nickel-based binding phase and a ceramic hard phase, and is widely applied to the fields of aerospace, aviation, energy power and the like. The traditional preparation method of the molybdenum nickel boron cermet is a powder metallurgy process, and the mechanical property of the material is reduced due to the fact that the grain structure is relatively large and the sintering porosity is high after sintering. Therefore, a new method is found, the problems of large grain structure and high porosity of the molybdenum-nickel-boron cermet are solved, and the important importance is to improve the service performance of the molybdenum-nickel-boron cermet.

The aims of refining and directionally distributing metal ceramic grains are fulfilled through surface activation, pack rolling and heat treatment of the metal foil, and the performance of the metal ceramic is further improved.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a preparation method of molybdenum-nickel-boron cermet, which is simple in process and has ultra-fine grain and tissue directional distribution and good mechanical properties.

The invention is realized by the following technical scheme.

An ultra-fine grain oriented distribution molybdenum-nickel-boron cermet material and a preparation method thereof comprise the following steps:

1) roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil;

2) activating the two sides of the nickel-boron foil and the nickel foil, and then cleaning;

3) sequentially laminating and rolling the molybdenum foil, the nickel foil and the nickel-boron foil according to the nickel foil, the molybdenum foil, the nickel-boron foil, the nickel foil, the molybdenum foil, the nickel-boron foil … …, the nickel foil, the molybdenum foil, the nickel-boron foil and the nickel foil, controlling the rotating speed and the rolling temperature of the roller, and accumulating and laminating for 30-80 layers;

4) and carrying out non-pressure heat treatment on the metal ceramic formed by the stack rolling, controlling the heat treatment temperature and the vacuum degree, and cooling after the non-pressure heat treatment to obtain the metal ceramic material with ultra-fine grains and directionally distributed structures.

With respect to the above technical solutions, the present invention has a further preferable solution:

preferably, the purity of the molybdenum foil, the nickel-boron foil and the nickel foil is not lower than 99.9%, the thickness of the molybdenum foil and the nickel-boron foil is not more than 0.1mm, and the thickness of the nickel foil is 1 mm.

Preferably, the surfaces of the molybdenum foil, the nickel foil and the nickel boron foil are roughened so that the thickness is controlled to be 0.1 μm < Ra < 1.0. mu.m.

Preferably, hydrochloric acid and nitric acid solutions with the mass ratio of 2:1 are used for double-sided activation of the molybdenum foil, concentrated hydrochloric acid and concentrated nitric acid solutions with the mass ratio of 3:1 are used for double-sided coating activation of the nickel-boron foil and the nickel foil, and then absolute ethyl alcohol is used for cleaning.

Preferably, the rolling process is as follows: the rotating speed of the roller is 0.1-0.5 m/min, and the rolling temperature is 850-950 ℃.

Preferably, the metal ceramic formed by stack rolling is placed into a vacuum heat treatment furnace for pressureless heat treatment.

Preferably, the heating rate of the heat treatment is 5-10 ℃/min, the temperature is increased to 600-800 ℃, and the vacuum degree is less than or equal to 10^{- 2}Pa; the cooling speed is 3-10 ℃/min, and the temperature is reduced to the room temperature.

Due to the adoption of the technical scheme, the invention has the following beneficial effects:

the molybdenum-nickel-boron cermet prepared by the method of roll-lamination forming and sintering can effectively control the continuity of a nickel-based binder phase in the cermet material, improve the relative density, and has excellent main mechanical performance indexes (the highest density reaches 99.1 percent, the highest bending strength reaches 2188MPa, and the highest fracture toughness reaches 30.0 MPa.m^1/2The highest hardness reaches 87HRA), and the oxidation resistance at 800-1000 ℃ is evaluated as complete oxidation resistance.

The method firstly selects molybdenum foil, nickel-boron foil and nickel foil with the purity of not less than 99.9 percent as main raw materials, and requires that the thickness of the molybdenum foil and the nickel-boron foil is not more than 0.1mm and the thickness of the nickel foil is about 1 mm. In the preparation process, the molybdenum foil, the nickel foil and the nickel-boron foil are subjected to surface roughening and double-sided activation treatment, so that the reaction activity is favorably ensured, the directional distribution of the structure of a generated phase can be controlled, and the molybdenum-nickel-boron metal ceramic material with excellent mechanical property indexes is obtained; the plasticity and the strength of the molybdenum-nickel-boron metal ceramic can be adjusted by adjusting the thickness of the nickel foil.

The molybdenum-nickel-boron cermet material prepared by the method has controllable phase composition distribution, high mechanical property and good high-temperature oxidation resistance by carrying out the pack rolling process according to a certain sequence.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:

FIG. 1 is an SEM image of a Mo-Ni-B cermet prepared in example 1 of the present invention.

Detailed Description

The invention will be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the invention are provided to explain the invention.

The ultra-fine grain oriented distribution molybdenum-nickel-boron cermet material and the preparation method thereof comprise the following steps:

1) the purity of the molybdenum foil, the nickel-boron foil and the nickel foil is not lower than 99.9 percent, the thickness of the molybdenum foil and the nickel-boron foil is not more than 0.1mm, and the thickness of the nickel foil is 1 mm. Roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil, wherein the Ra is controlled to be less than 0.1 mu m and less than 1.0 mu m;

2) performing double-sided activation on the molybdenum foil by adopting hydrochloric acid and nitric acid solutions with the mass ratio of 2:1, performing double-sided coating activation on the nickel-boron foil and the nickel foil by adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the mass ratio of 3:1, and then cleaning by using absolute ethyl alcohol;

3) sequentially and cumulatively rolling the nickel foil, the molybdenum foil, the nickel-boron foil, the nickel foil, the molybdenum foil, the nickel-boron foil … …, the nickel foil, the molybdenum foil, the nickel-boron foil and the nickel foil in sequence, controlling the rotating speed of a roller to be 0.1-0.5 m/min, the rolling temperature to be 850-950 ℃ and cumulatively rolling for 30-80 layers;

4) pressureless rolling the metal ceramicHeat treatment, controlling the temperature rise speed of the heat treatment to be 5-10 ℃/min, raising the temperature to 600-800 ℃, and controlling the vacuum degree to be less than or equal to 10^-2Pa; and (3) cooling after non-pressure heat treatment, wherein the cooling speed is 3-10 ℃/min, and the temperature is reduced to room temperature, so that the cermet material with ultra-fine grains and directionally distributed structures is obtained.

The invention is further illustrated by the following specific examples.

Example 1:

(1) selecting molybdenum foil, nickel-boron foil and nickel foil with the purity of not less than 99.9% as main raw materials, wherein the thicknesses of the molybdenum foil, the nickel-boron foil and the nickel foil are required to be not more than 0.1 mm; roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil, wherein Ra is controlled to be 0.1 mu m;

(2) respectively adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the mass ratio of 2:1 to perform double-sided activation on the molybdenum foil, adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the mass ratio of 3:1 to perform double-sided coating activation on the nickel-boron foil and the nickel foil, and then cleaning with absolute ethyl alcohol;

(3) sequentially accumulating and rolling 30 layers of nickel foils (1mm), molybdenum foils, nickel-boron foils, nickel foils, molybdenum foils, nickel-boron foils … … according to the sequence of the nickel foils (1mm), the molybdenum foils, the nickel-boron foils, the nickel foils, the molybdenum foils, the nickel-boron foils and the nickel foils (1mm), wherein the rolling process comprises the following steps: the rotating speed of the roller is 0.1m/min, and the rolling temperatures are 900 ℃ respectively;

(4) the metal ceramic formed by the stack rolling is put into a vacuum heat treatment furnace for non-pressure heat treatment, the heat treatment temperature is 800 ℃, the temperature rising speed is 7 ℃/min, the vacuum degree is less than or equal to 10^-2Pa, and the cooling speed is 3 ℃/min, thus obtaining the cermet material with ultra-fine grains and oriented structure distribution.

The SEM image of the prepared Mo-Ni-B cermet is shown in FIG. 1.

Example 2

(1) Selecting molybdenum foil, nickel-boron foil and nickel foil with the purity of not less than 99.9% as main raw materials, wherein the thicknesses of the molybdenum foil, the nickel-boron foil and the nickel foil are required to be not more than 0.1 mm; roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil, wherein Ra is controlled to be 1.0 mu m;

(2) respectively adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the ratio of 2:1 to perform double-sided activation on the molybdenum foil, adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the ratio of 3:1 to perform double-sided activation on the nickel-boron foil and the nickel foil, and then cleaning with absolute ethyl alcohol;

(3) the 80 layers of nickel foil (1mm), molybdenum foil, nickel boron foil, nickel foil, molybdenum foil, nickel boron foil … … nickel foil, molybdenum foil, nickel boron foil, nickel foil, molybdenum foil, nickel boron foil and nickel foil (1mm) are accumulated and rolled in sequence, and the rolling process is as follows: the rotating speed of the roller is 0.3m/min, and the rolling temperature is 950 ℃;

(4) the metal ceramic formed by the stack rolling is put into a vacuum heat treatment furnace for non-pressure heat treatment, the heat treatment temperature is 600 ℃, the temperature rising speed is 10 ℃/min, the vacuum degree is less than or equal to 10^-2Pa, cooling at the speed of 10 ℃/min to room temperature to obtain the cermet material with ultra-fine grains and oriented structure distribution.

Example 3

(1) Selecting molybdenum foil, nickel-boron foil and nickel foil with the purity of not less than 99.9% as main raw materials, wherein the thicknesses of the molybdenum foil, the nickel-boron foil and the nickel foil are required to be not more than 0.1 mm; roughening the surfaces of the molybdenum foil, the nickel foil and the nickel-boron foil, wherein Ra is controlled to be 0.5 mu m;

(2) respectively adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the ratio of 2:1 to perform double-sided activation on the molybdenum foil, adopting concentrated hydrochloric acid and concentrated nitric acid solutions with the ratio of 3:2 to perform double-sided activation on the nickel-boron foil and the nickel foil, and then cleaning with absolute ethyl alcohol;

(3) accumulating and rolling 60 layers according to the sequence of nickel foil, molybdenum foil, nickel boron foil, nickel foil, molybdenum foil, nickel boron foil … … nickel foil, molybdenum foil, nickel boron foil, nickel foil, molybdenum foil, nickel boron foil and nickel foil (1mm), wherein the rolling process comprises the following steps: the rotating speed of the roller is 0.5m/min, and the rolling temperatures are respectively 850 ℃;

(4) the metal ceramic formed by the stack rolling is put into a vacuum heat treatment furnace for non-pressure heat treatment, the heat treatment temperature is 700 ℃, the temperature rising speed is 5 ℃/min, the vacuum degree is less than or equal to 10^-2Pa, and the cooling speed is 8 ℃/min, thus obtaining the cermet material with ultra-fine grains and oriented structure distribution.

The performance parameters of the ultrafine grain oriented molybdenum nickel boron cermet materials prepared in the embodiments 1-3 are shown in Table 1:

TABLE 1 Properties of the examples

As can be seen from the above table, the fracture toughness of the ultra-fine grain oriented molybdenum-nickel-boron cermet material prepared by the embodiment of the invention is not lower than 28.6 MPa.m^1/2The hardness is not lower than HRA85, the bending strength is not lower than 1970MPa, and the high-temperature oxidation resistance is evaluated as a complete oxidation resistance level.

The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.