阅读说明：本技术 一种硫代钼酸铵复合多孔非晶碳超滑薄膜的制备方法 (Preparation method of ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film ) 是由 张斌 贾倩 张俊彦 于元烈 高凯雄 张兴凯 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种硫代钼酸铵复合多孔非晶碳超滑薄膜的制备方法,先采用阳极层离子源辅助等离子体化学气相沉积方法和反应磁控溅射法在基体上制备非晶多孔碳薄膜,再将非晶多孔碳薄膜浸渍在硫代钼酸铵溶液中,使硫代钼酸铵被吸附非晶多孔碳薄膜上,自然风干即得。本发明制备的复合多孔非晶碳超滑薄膜在摩擦过程中,利用磨合初期摩擦热的作用,促使硫代钼酸铵原位分解形成二硫化钼,并进一步催化形成类石墨烯结构,然后通过石墨烯和二硫化钼的异质非公度接触,最终实现宏观超滑。另外,硫代钼酸铵通过液相浸渍到非晶多孔碳薄膜上,自然风干后形成的薄膜具有良好的均匀性,具有很好的结合力,因此制备的复合多孔非晶碳超滑薄膜具有较长的使用寿命。(The invention discloses a preparation method of an ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film, which comprises the steps of preparing an amorphous porous carbon film on a substrate by adopting an anode layer ion source assisted plasma chemical vapor deposition method and a reactive magnetron sputtering method, dipping the amorphous porous carbon film in an ammonium thiomolybdate solution to enable ammonium thiomolybdate to be adsorbed on the amorphous porous carbon film, and naturally drying to obtain the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film. In the friction process of the composite porous amorphous carbon ultra-smooth film prepared by the invention, the action of friction heat in the initial stage of running-in is utilized to promote ammonium thiomolybdate to be decomposed in situ to form molybdenum disulfide, and further catalysis is carried out to form a graphene-like structure, and then the macroscopic ultra-smooth is finally realized through heterogeneous non-degree contact of graphene and molybdenum disulfide. In addition, ammonium thiomolybdate is impregnated on the amorphous porous carbon film through a liquid phase, and the film formed after natural air drying has good uniformity and good binding force, so that the prepared composite porous amorphous carbon ultra-smooth film has longer service life.)

1. A preparation method of an ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film comprises the following steps:

(1) the preparation of the high-bonding-force transition layer comprises ultrasonically cleaning the substrate, placing in a vacuum chamber, and pumping the vacuum chamber to 1 × 10^{- 3}Pa, magnetron sputtering ti0.7ni0.3 target: magnetron sputtering current 5A, ion source voltage 1300-; then introducing nitrogen with 13 percent of argon, keeping the conditions unchanged, depositing for 40 minutes, and obtaining a transition layer on the substrate;

(2) preparing an amorphous porous carbon film: preparing an amorphous porous carbon film by adopting reactive magnetron sputtering, adopting an aluminum-carbon composite target containing 10% of aluminum, wherein the reaction gas is argon, carbon tetrafluoride, hydrogen and oxygen, the flow ratio is 2:1:1:0.2, and the air pressure is kept at 1-3 Pa; magnetron sputtering current 4A; the deposition time is 40-60 minutes, and a porous carbon film is obtained;

(3) preparation of ammonium tetrathiomolybdate solution: dissolving ammonium thiomolybdate solid powder in deionized water, and performing ultrasonic magnetic stirring to obtain an ammonium thiomolybdate solution with the concentration of 1-3%;

(4) preparing an ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film: and (2) immersing the amorphous porous carbon film prepared in the step (1) in an ammonium thiomolybdate solution, keeping for 4-5 hours, taking out and naturally drying to obtain the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film.

2. The method for preparing the ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the substrate is one of stainless steel, gear steel and bearing steel.

3. The method for preparing the ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the ammonium thiomolybdate is one of ammonium trithiomolybdate, ammonium tetrathiomolybdate and ammonium pentathiomolybdate.

4. The method for preparing the ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the ultrasonic power is 500W, the frequency is 200Hz, and the rotating speed is 10 circles/minute.

Technical Field

The invention relates to a composite super-smooth film, in particular to a preparation method of an ammonium thiomolybdate composite porous amorphous carbon super-smooth film, and belongs to the technical field of vacuum coating and tribology.

Background

Friction is a common problem for mechanical systems, friction consumes more than 30% of the disposable energy, and wear consumes 60% of the failure of mechanical parts. With the development of industrial upgrading in China, energy conservation, emission reduction, high reliability, long service life and the like of equipment such as automobiles, airplanes, equipment manufacturing, aerospace and the like are closely related to the high-performance solid lubricating material. Among them, the demand of the automobile, heavy machinery, aviation and aerospace for the high-performance lubricating material technology is particularly urgent. For example, key components such as piston rings, valves, tappets, camshafts and piston pins of engines, components such as plungers and needle valves of fuel injection systems, and basic components such as key components of systems such as hydraulic power steering systems, turbine compression systems, aerospace system bearings, flywheels and moment gyros of airplanes are deficient in research on tribology mechanisms, materials and technologies, and upgrade and update and performance improvement of high-end equipment in China are severely restricted.

In general, the lubricating oil has a friction coefficient of about 0.05, and the super-lubricity refers to a state where the friction coefficient is in the order of 0.001 or less. The practical application of the ultra-smooth structure greatly reduces the friction power consumption and the abrasion, not only improves the energy utilization efficiency, but also can prolong the service life of the moving part and improve the reliability. CN201910688409.X provides a method for realizing ultra-smoothness between an AFM probe with a conical tip and a graphite surface, and can realize ultra-smoothness of a micrometer size with a friction coefficient as low as 0.001. CN201510582261.3 provides a preparation method of a magnetron sputtering silver-containing graphite-like carbon film with an ultra-low friction coefficient, but the actual friction coefficient is more than 0.01, and ultra-smoothness (ultra-low friction) in the true sense is not realized. CN201710403632.6 provides a macroscopic super-smooth method for growing graphene on a friction surface, the friction coefficient is stabilized at 0.003-0.008, but the graphene can only grow on the surface of catalytic metal such as nickel iron and the like, and the engineering application of the graphene is limited. CN201110277261.4 provides a diamond-like carbon composite molybdenum disulfide nano multilayer film and a preparation method thereof, which claims to realize an ultralow friction coefficient (0.02-0.03) in an atmospheric environment, but the friction coefficient range defined by ultra-smoothness is 1 order of magnitude different. Therefore, a solid lubricating film material with lower friction coefficient and less energy consumption is needed.

Disclosure of Invention

The invention aims to provide a preparation method of an ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film.

Preparation of ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film

The preparation method of the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film comprises the following steps:

(1) the preparation of the high-bonding-force transition layer comprises ultrasonically cleaning the substrate, placing in a vacuum chamber, and pumping the vacuum chamber to 1 × 10^{- 3}Pa, magnetron sputtering ti0.7ni0.3 target: magnetron sputtering current 5A, ion source voltage 1300-; then, 13% argon gas and nitrogen gas are introduced, the conditions are kept unchanged, the deposition time is 40 minutes, and a transition layer is obtained on the substrate. The substrate is one of stainless steel, gear steel and bearing steel.

(2) Preparing an amorphous porous carbon film: preparing an amorphous porous carbon film by adopting reactive magnetron sputtering, adopting an aluminum-carbon composite target containing 10% of aluminum, wherein the reaction gas is argon, carbon tetrafluoride, hydrogen and oxygen, the flow ratio is 2:1:1:0.2, and the air pressure is kept at 1-3 Pa; magnetron sputtering current 4A; depositing for 40-60 minutes to obtain the porous carbon film with the diameter of the micropores being 20-40 nm.

(3) Preparation of ammonium tetrathiomolybdate solution: dissolving ammonium thiomolybdate solid powder in deionized water, and performing ultrasonic magnetic stirring to obtain an ammonium thiomolybdate solution with the concentration of 1-3%; ultrasonic power 500W, frequency 200Hz, and rotation speed 10 circles/minute. The ammonium thiomolybdate is one of ammonium trithiomolybdate, ammonium tetrathiomolybdate and ammonium pentathiomolybdate.

(4) Preparing an ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film: and (2) immersing the amorphous porous carbon film prepared in the step (1) in an ammonium thiomolybdate solution with the concentration of 1-3%, keeping for 4-5 hours, taking out and naturally drying to obtain the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film. In the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film, ammonium thiomolybdate is deposited on the nano-pores and the surface.

Friction performance of ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film

Taking ammonium tetrathiomolybdate composite porous amorphous carbon super-smooth film as an example, a friction experiment was performed under the conditions of a load of 5N, a frequency of 5Hz, a dual ball diameter of 6mm, a time of 30min, and a reciprocating distance of 5 mm. The results are shown in FIG. 1, which has an average coefficient of friction of 0.0057, and completely achieved super-lubricity.

Experiments show that the ammonium thiomolybdate composite porous amorphous carbon ultra-smooth film obtained by replacing ammonium tetrathiomolybdate with ammonium tri-and penta-thiomolybdate also realizes ultra-smoothness.

The invention realizes the principle of ultra-lubricity: in the friction process of the composite porous amorphous carbon ultra-smooth film prepared by the invention, the action of friction heat in the initial stage of running-in is utilized to promote ammonium thiomolybdate to be decomposed in situ to form molybdenum disulfide, and further catalysis is carried out to form a graphene-like structure, and then the macroscopic ultra-smooth is finally realized through heterogeneous non-degree contact of graphene and molybdenum disulfide. In addition, ammonium thiomolybdate is impregnated on the amorphous porous carbon film through a liquid phase, and the film formed after natural air drying has good uniformity and good binding force, so that the prepared composite porous amorphous carbon ultra-smooth film has longer service life.

Drawings

FIG. 1 is a surface structure diagram of an ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film prepared by the present invention.

FIG. 2 is a friction curve of the ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film prepared by the present invention.

Detailed Description

The preparation and performance of the ammonium tetrathiomolybdate composite porous amorphous carbon ultra-smooth film of the present invention are further described by the following specific examples.