Search

CN-117604446-B - High-entropy carbon nitride ceramic composite coating and preparation method thereof

CN117604446BCN 117604446 BCN117604446 BCN 117604446BCN-117604446-B

Abstract

A high-entropy carbon nitride compound ceramic composite coating is characterized by sequentially comprising a high-entropy alloy carbon nitride reaction deposition layer, a carbon nitrogen diffusion layer, a high-entropy alloy layer and an alloy diffusion layer from outside to inside, wherein the molecular formula of the high-entropy alloy carbon nitride reaction deposition layer is (Ti a V b Cr c Si d X e Y f )(C g N h ), and the molecular formula of the high-entropy alloy layer is Ti a V b Cr c Si d X e Y f . The invention also discloses a preparation method of the composite coating. The high-entropy carbon nitride ceramic composite coating has self-healing capability and anti-stripping capability in different temperature ranges.

Inventors

  • CHEN XIAOHU
  • HAN JUNGANG
  • JIANG KEMING
  • YIN FEI
  • XU YONGDONG
  • REN ZHENG

Assignees

  • 中国兵器科学研究院宁波分院
  • 陆军装备部驻南京地区军事代表局驻烟台地区军事代表室

Dates

Publication Date
20260512
Application Date
20231107

Claims (10)

  1. 1. A high-entropy carbon nitride compound ceramic composite coating is characterized in that the composite coating sequentially comprises a high-entropy alloy carbon nitride reaction deposition layer, a carbon nitrogen diffusion layer, a high-entropy alloy layer and an alloy diffusion layer from outside to inside, The molecular formula of the high-entropy alloy carbonitride reaction deposition layer is (Ti a V b Cr c Si d X e Y f ) (C g N h ), the molecular formula of the high-entropy alloy layer is Ti a V b Cr c Si d X e Y f , Wherein a is more than or equal to 0.1 and less than or equal to 0.25 at%, b is more than or equal to 0.01 and less than or equal to 0.25 at%, C is more than or equal to 0.01 and less than or equal to 0.25 at%, d is more than or equal to 0.01 and less than or equal to 0.15 at%, e is more than or equal to 0.01 and less than or equal to 0.25 at%, f is more than or equal to 0.01 and less than or equal to 0.25at percent, and satisfies a+b+c+d+e+f=1, X and Y are one of Zr, nb, hf, ta, W respectively, C is carbon element, N is nitrogen element, g is more than or equal to 0.1 and less than or equal to 1 at%, h is more than or equal to 0.1 and less than or equal to 1 at%, and g+h=1 is satisfied.
  2. 2. The high entropy carbon nitride ceramic composite coating according to claim 1, wherein the high entropy alloy carbonitride reaction deposit layer is of a single face-centered cubic phase structure.
  3. 3. The high-entropy carbon nitride compound ceramic composite coating according to claim 1, wherein the thickness of the high-entropy alloy carbon nitride reaction deposition layer is 10-40 μm, the thickness of the carbon nitrogen diffusion layer is 2-5 μm, the thickness of the high-entropy alloy layer is 5-20 μm, and the thickness of the alloy diffusion layer is 2-5 μm.
  4. 4. The high-entropy carbon nitride compound ceramic composite coating according to claim 1, wherein the carbon nitrogen content in the high-entropy alloy carbon nitride reaction deposition layer is distributed in a gradient manner and gradually decreases from outside to inside.
  5. 5. A method for preparing the high-entropy carbon nitride compound ceramic composite coating according to any one of claims 1 to 4, which is characterized by comprising the following steps in sequence: (1) Pre-grinding, polishing and cleaning the surface of the matrix material, and performing sputtering pretreatment; (2) Placing TiVCrSiXY high-entropy alloy targets and graphite targets in an arc glow plasma metal infiltration device, taking a base material as a workpiece electrode, and taking the high-entropy alloy targets and the graphite targets as source electrodes; (3) Vacuumizing, feeding argon, starting glow, debugging the power supply and current process parameters of the workpiece and the high-entropy alloy target material, and completing the preparation of the high-entropy alloy coating; (4) Introducing ammonia gas, and debugging the process parameters of the workpiece, the graphite target power supply and the current to finish the preparation of the carbon-nitrogen diffusion layer; (5) Introducing ammonia gas, and debugging the process parameters of the power supply and current of the workpiece, the high-entropy alloy target and the graphite target to finish the preparation of the high-entropy alloy carbonitride reaction deposition layer; stopping glow, powering off, and adjusting vacuum to atmospheric pressure to finish the preparation of the high-entropy carbon-nitrogen compound ceramic composite coating to obtain the ablation-resistant composite coating with the wide-temperature-range self-healing characteristic.
  6. 6. The method of manufacturing according to claim 5, wherein in the step (1), the substrate is used as a workpiece electrode during the sputtering pretreatment, the source voltage and the current are set to zero, the workpiece voltage is set to 500-700V, the workpiece current is set to 0.1A-0.3A, and simultaneously high-purity argon gas is introduced at an argon gas pressure of 20-60 Pa for 0.5-2 hours.
  7. 7. The method of claim 5, wherein in the step (2), 0.01-0.02 at.% of iridium is added to the TiVCrSiXY-system high-entropy alloy target.
  8. 8. The method according to claim 5, wherein in the step (3), the high-entropy alloy target material has a voltage of 700-950V, a workpiece voltage of 400-650V, an argon gas pressure of 25-45 Pa, a polar distance between the target material and the workpiece of 10-25 mm, a heat preservation time of 4-8 h and a treatment temperature of 600-1100 ℃.
  9. 9. The preparation method of the graphite electrode material, which is characterized in that in the step (4), ammonia gas and argon gas are introduced to enable the flow ratio to be 4:1, the stable air pressure is 40-50 Pa, the debugging process parameters are that the graphite target material voltage is 700-650V, the workpiece voltage is 400-650V, the polar distance between the target material and the workpiece is 15-20 mm, the heat preservation time is 4-5 h, and the processing temperature is 800-1000 ℃.
  10. 10. The preparation method of the high-entropy alloy is characterized in that in the step (5), ammonia gas and argon gas are introduced to enable the flow ratio to be 2:1, the stable air pressure is 30-45 Pa, the debugging process parameters are that the graphite target voltage is 700-950V, the high-entropy alloy target voltage is 700-1000V, the workpiece voltage is 400-650V, the polar distance between the target and the workpiece is 15-20mm, the heat preservation time is 5-8 h, and the treatment temperature is 700-1000 ℃.

Description

High-entropy carbon nitride ceramic composite coating and preparation method thereof Technical Field The invention relates to a composite coating, which is applied to a thermal protection material, and a preparation method of the composite coating. Background In the process of firing of the cannon, the barrel inner bore is in a complex state of high temperature and high pressure and is accompanied by transient high-speed impact and abrasion, and the improvement of the ablation resistance becomes a key problem for limiting the life of the barrel. The problems of easy flaking and crack of the active electroplated Cr mainly exist. Aiming at the difficult problem, the research on Cr electroplating and Ta magnetron sputtering processes is mainly carried out in China, but the research is limited by taking metal elements as main components and a single coating structure, and the metal coating has theoretical limit on service performance and service life and has limited lifting potential. While the hot end component of the high-performance aeroengine needs to meet the performance requirements of long service life, wide temperature range oxidation resistance, scouring resistance, fatigue vibration resistance and the like, the heat protection system of the hypersonic aerospace craft needs to bear serious ablation, high-speed airflow strong scouring, large-gradient thermal shock and the like in the service process. Carbon-based composite materials represented by graphite and carbon/carbon (C/C) composite materials have high-temperature oxidation sensitivity and insufficient ablation resistance, and severely restrict the application of the carbon-based composite materials as thermal structural materials. The coating technology is an effective means for improving the oxidation/ablation resistance of the C/C composite material. In order to cope with the above extreme environments, there is a need to develop a thermal protection material with high performance, that is, a wide temperature range high temperature protection material with oxidation resistance, ablation resistance and excellent thermal shock resistance, which is used for a long time under the atmospheric working condition of up to 1200-2500 k. High entropy ceramics (high entropy ceramics, HECs), also known as multi-principal component, equal atomic ratio or near equal atomic ratio multi-component ceramics, are novel ceramic materials which are developed recently. Compared with the traditional ceramic, the high-entropy ceramic has four characteristics of (1) multiple principal elements. Comprises a plurality of main constituent elements, wherein the main elements are mixed in an equal atomic ratio or a near equal atomic ratio, and the atomic percentage content of each main element is between 5 and 35 percent. (2) high entropy effects. The high entropy ceramic has a much higher configurational entropy than conventional ceramics, and thus its solidification structure readily obtains a single-phase disordered solid solution structure (including face-centered cubic FCC, body-centered cubic BCC, and close-packed hexagonal HCP). (3) lattice distortion effects. Multiple atoms with different atomic sizes are randomly distributed on the same lattice, which tends to cause serious distortion of the lattice. (4) slow diffusion effect. The complexity and severe lattice distortion of the chemical composition makes diffusion of atoms inside the high entropy ceramic exceptionally difficult. The synergistic effect of the characteristics ensures that the high-entropy ceramic has a series of excellent mechanical, physical and chemical properties, and has wide application prospect in the aspects of high strength, high hardness, high wear resistance, high corrosion resistance, high-temperature softening resistance, low thermal conductivity, excellent soft magnetism and the like. So far, in the field of ablation resistant ceramic coatings, high entropy ceramics are not well defined and less studied. The high-entropy alloy concept is used for synthesizing high-entropy oxygen compound ceramic (Entropy-stabilized oxides [ J ]. Nature communications.2015, 6:8485) for the first time by Rost et al at Duke university, but only the role of researching entropy in forming a single phase is not related to performance improvement caused by four major effects brought by high entropy, and subsequently, the high-entropy alloy concept is used for synthesizing high-entropy ultrahigh-temperature ceramic (High-Entropy Metal Diborides:ANew Class of High-Entropy Materials and a New Type of Ultrahigh Temperature Ceramics[J].Scientific Reports.2016,6:37946), by using the high-entropy alloy concept by Ind university Gild et al at California, namely, adding various other elements similar to matrix elements into an original binary ultrahigh-temperature ceramic matrix, and forming a compound with a single solid solution structure, namely, the high-entropy ultrahigh-temperature ceramic. The research finds that