CN-122013113-A - Amorphous-nanocrystalline composite structure high-entropy nitride film and preparation method thereof

CN122013113ACN 122013113 ACN122013113 ACN 122013113ACN-122013113-A

Abstract

The invention provides an amorphous-nanocrystalline composite structure high-entropy nitride film and a preparation method thereof, and relates to the technical field of film materials. The multi-arc ion plating technology and the high-power pulse magnetron sputtering technology are adopted, and the (Ti/TiN.)/(nc-HEAN/a-Si 3N 4) multilayer nano composite structure high-entropy film is prepared through component proportioning and structure regulation. The nano multilayer structure can realize the advantages of deflection of cracks at the interface, passivation of crack tips at the interface, prevention of initiation and expansion of microcracks caused by stress concentration, and the like. The nanocrystalline nc-HEAN high-entropy nitride is inlaid in amorphous a-Si3N4 to form a nanocrystalline/amorphous multiphase composite structure. By means of the nano multilayer structure and the nanocrystalline/amorphous multiphase composite structure, the multilayer nano composite high-entropy nitride film with high hardness/high toughness is prepared, so that the requirements of the modern industrial technology on the high-performance application of cutters and grinding tools are met.

Inventors

FENG XINGGUO
Yang Lamao grass
ZHANG KAIFENG
ZHOU HUI
ZHANG YANSHUAI
ZHENG YUGANG
WANG KELIANG

Assignees

兰州空间技术物理研究所

Dates

Publication Date: 20260512
Application Date: 20251111

Claims (11)

1. The amorphous-nanocrystalline composite structure high-entropy nitride film is characterized by comprising soft-hard alternating transition layers and superhard high-entropy nitride layers, wherein, The soft and hard alternating transition layers are coated on the surface of the metal substrate, the superhard high-entropy nitride layer is coated on the surface of the soft and hard alternating transition layers, The soft-hard alternating transition layer comprises N first layers and N second layers, the N first layers and the N second layers are alternately stacked, the N first layers are close to the metal substrate, and the N second layers are far away from the metal substrate.
2. The amorphous-nanocrystalline composite structure high-entropy nitride film according to claim 1, wherein the raw materials of the soft-hard alternate transition layer comprise Ti and TiN, the first layer is a Ti layer, and the second layer is a TiN layer.
3. The amorphous-nanocrystalline composite structure high-entropy nitride film according to claim 1, wherein the super-hard high-entropy nitride layer comprises nc- (ALTICRVTA) N/a-Si 3 N 4 , raw materials of the super-hard high-entropy nitride layer comprise metal elements and nonmetal elements, the metal elements comprise Al, ti, cr, V, ta, the metal elements comprise Al, cr, V and Ta in an atomic ratio of 1:1:1:1:1, the nonmetal elements comprise Si and N, and the doping amount of the Si elements accounts for 5-10at% of the total content of the high-entropy nitride film.
4. The amorphous-nanocrystalline composite structure high-entropy nitride film according to claim 1, wherein the thickness of each layer of the soft-hard alternating transition layers is 5-10 nm, the total thickness of the soft-hard alternating transition layers is 200-500 nm, the thickness of the superhard high-entropy nitride layer is 800-1500 nm, and the thickness of the amorphous-nanocrystalline composite structure high-entropy nitride film is 1000-2000 nm.
5. The amorphous-nanocrystalline composite structure high-entropy nitride film according to claim 1, wherein the metal matrix is WC-Co cemented carbide, titanium alloy or high-speed steel.
6. The method for preparing the amorphous-nanocrystalline composite structure high-entropy nitride film according to any one of claims 1 to 5, which is characterized by comprising the following steps: step (1) carrying out chemical cleaning on the surface of a metal matrix to remove pollutants on the surface layer; step (2) putting the metal matrix into a vacuum chamber for plasma sputtering treatment; Preparing soft and hard alternating transition layers on the surface of the metal matrix by adopting an arc ion plating technology; and (4) preparing a superhard high-entropy nitride layer on the surface of the soft-hard alternating transition layer by adopting a high-power pulse magnetron sputtering technology.
7. The preparation method of the metal substrate according to claim 6, wherein in the step (1), the surface of the metal substrate is subjected to chemical cleaning to remove pollutants on the surface layer, and the method comprises the steps of sequentially placing the metal substrate in acetone and alcohol solution, respectively cleaning the metal substrate for 5-10 min by adopting ultrasonic waves, and then drying by adopting dry nitrogen.
8. The method according to claim 6, wherein in the step (2), the plasma sputtering treatment comprises introducing argon gas, and performing plasma glow discharge sputtering on the metal substrate for 15-20 min.
9. The method according to claim 6, wherein in the step (3), the arc ion plating technique is used to prepare soft-hard alternating transition layers on the surface of the metal substrate, comprising: The process conditions of preparing the Ti layer by adopting arc ion plating are that argon is used as working gas, the argon pressure is 0.3-0.6 Pa, the direct current bias voltage of a substrate is-50-100V, the Ti target current is 60-80A, and the thickness of the Ti layer is controlled to be 5-10 nm; the method comprises the steps of (31) preparing a TiN layer by adopting arc ion plating, wherein the process conditions are that nitrogen and argon are introduced, the flow ratio of the nitrogen to the argon is 1:4, the direct current bias voltage of a substrate is-50 to-150V, the purity of a Ti target is more than or equal to 99.9%, the current of the Ti target is 70-90A, and the thickness of the TiN layer is controlled to be 5-10 nm; and (32) sequentially and alternately executing the step (30) and the step (31) until the thickness of the prepared Ti/TiN soft and hard alternate transition layer reaches 200-500 nm.
10. The method according to claim 6, wherein in the step (4), the high-power pulse magnetron sputtering is performed under the process conditions that argon is used as a working gas, the argon pressure is 0.5-1.0 Pa, the substrate direct current bias voltage is-50 to-150V, a ALTICRVTA high-entropy alloy target and a Si target are adopted, the purity of the ALTICRVTA high-entropy alloy target is more than or equal to 99.5%, the power is 1.5-2.0 kW, the purity of the Si target is more than or equal to 99.9%, the power is 0.2-0.5 kW, and the thickness of the high-entropy nitride layer is controlled to 800-1500 nm.
11. The method of claim 6, wherein steps (2), (3) and (4) are performed continuously in the same equipment chamber, wherein the ALTICRVTA high-entropy alloy target and the Si target are installed at a high-power target cathode position, and wherein the Ti target is installed at an arc ion plating cathode position.

Description

Amorphous-nanocrystalline composite structure high-entropy nitride film and preparation method thereof Technical Field The invention relates to the technical field of film materials, in particular to an amorphous-nanocrystalline composite structure high-entropy nitride film and a preparation method thereof. Background The surface protection technology of the cutter and the die is rapidly developed along with the industry upgrading and the advancement of material science, and the surface protection technology is required to be far superior to the common product in the aspects of performance, service life, precision and applicability, and the advanced surface technology can not only remarkably prolong the service life of the cutter and the grinding tool and improve the processing precision, but also break through the limitation of the traditional materials and adapt to extreme application scenes. Binary and ternary Transition Metal Nitrides (TMNs) have good mechanical properties, thermal stability and excellent chemical inertness, are widely applied to the field of hard coating protection of cutters, grinding tools and the like, but have the problems of insufficient hardness and toughness, low film-based binding force and the like, and gradually cannot meet the increasingly complex working condition demands. Compared with the traditional nitride film, the high-entropy nitride film has improved hardness, high elastic modulus and wear resistance to a certain extent. Patent application numbers CN202210305161.6 and CN202410451301.X report a TiAlMoNbW high-entropy alloy nitride film and a preparation process thereof, a TiAlNbTaW high-entropy alloy nitride film and a preparation method and application thereof respectively, and the two patents adopt a magnetron sputtering technology to prepare the high-entropy nitride film, and the film layer has simple structure and simple preparation method. But the hardness of the film is between 20 GPa and 30 GPa, which is slightly higher than that of the traditional binary and ternary nitrides, and the film is difficult to meet the requirements of high-end industrial application. The patent with the application number of CN2024101112557.8 reports a hard high-entropy alloy nitride film material and a preparation method thereof, and the hardness of the high-entropy nitride film prepared by the patent is up to 48 GPa, but the toughness of the film is not reported, and the method for improving the toughness and the adhesive force of the film is not described. The hardness of the nitride film reported in the review paper （Li Wei, Liu Ping, Liaw Peter K, Microstructures and properties of high-entropy alloy films and coatings: a review [J], Materials Research Letters, 2018, 6: 199-229） is 10 GPa-66 GPa, the mechanical properties of the nitride film are influenced by the element composition and content, the film structure of the film layer, the preparation process and the like, and the toughness of the ultra-high hardness film is an important factor influencing the film base binding force and tribological properties of the ultra-high hardness film. Therefore, developing a high-entropy nitride film with high hardness and high toughness expands the industrial application of the film and becomes a technical problem to be solved urgently by those skilled in the art. Disclosure of Invention Therefore, the invention provides the amorphous-nanocrystalline composite structure high-entropy nitride film and the preparation method thereof, the characteristic of high toughness integration is realized through the amorphous-nanocrystalline composite structure, the hardness and toughness of the high-entropy nitride film can be obviously improved, the wear rate is reduced, and the high-performance application requirements of modern industrial technology on cutters and grinding tools are met. In order to achieve the above purpose, the present invention provides the following technical solutions: In a first aspect, the invention provides an amorphous-nanocrystalline composite structure high-entropy nitride film, which comprises soft and hard alternating transition layers and superhard high-entropy nitride layers, wherein the soft and hard alternating transition layers are coated on the surface of a metal substrate, the superhard high-entropy nitride layers are coated on the surface of the soft and hard alternating transition layers, the soft and hard alternating transition layers comprise N first layers and N second layers, the N first layers and the N second layers are alternately laminated, the N first layers are close to the metal substrate, and the N second layers are far away from the metal substrate. Further, the metal matrix is WC-Co hard alloy, titanium alloy or high-speed steel. Further, the raw materials of the soft-hard alternating transition layer comprise Ti and TiN. Further, the first layer is a Ti layer. Further, the second layer is a TiN layer. Further, the superhard high-entropy nitride