A high-temperature wear-resistant self-lubricating boron-doped diamond-like coating and its preparation method and application

Abstract

The present invention discloses a high temperature wear-resistant self-lubricating boron-doped diamond-like coating and its preparation method and application, belonging to the technical field of coating materials. The boron-doped diamond-like coating comprises a Cr base layer deposited on the surface of a substrate, a Cr x B y C z Gradient transition layer and B-DLC functional layer; Cr base layer thickness is 0.15μm~0.25μm, Cr mass percentage is 99.5%~99.99%; Cr x B y C z The gradient transition layer has a thickness of 0.05μm to 0.10μm, a Cr mass percentage greater than 0 and ≤ 99.99%, and a B mass percentage greater than 0 and ≤ 8%. The B-DLC functional layer has a thickness of 0.8μm to 2.0μm, and a B mass percentage of 3% to 5%. This boron-doped diamond-like coating combines high hardness, high toughness, and low friction, exhibiting excellent self-lubrication and wear resistance in high-temperature atmospheric environments of 400-500°C.

Description

Technical Field

[0001] The present invention relates to the technical field of coating materials, and in particular to a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating and a preparation method and application thereof. Background Art

[0002] Diamond-like carbon (DLC) is a solid lubricant material with both high hardness and low friction. It is currently widely used in many high-tech fields such as aerospace and automobiles. The unique physical and chemical properties of DLC coatings make it an ideal material for reducing friction and improving the durability of mechanical components. However, pure DLC coatings have problems such as poor toughness, poor thermal stability, and their tribological properties are sensitive to temperature changes in practical applications. These problems seriously limit their use in high-temperature and harsh environments. In particular, DLC coatings begin to undergo graphitization transformation when the temperature reaches about 300°C. This process causes significant degradation of their mechanical and tribological properties. Therefore, it is of great significance to improve the toughness and thermal stability of DLC films and reduce their sensitivity to temperature in order to expand the temperature range in which they can be used for lubrication.

[0003] In view of this, the present invention is proposed. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating and its preparation method and application, so as to solve or improve the above technical problems.

[0005] The present invention can be achieved like this:

[0006] In the first aspect, the present invention provides a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, which comprises a Cr base layer, a Cr x B y C z Gradient transition layer and B-DLC functional layer;

[0007] The Cr base layer has a columnar structure, and the thickness of the Cr base layer is 0.15μm to 0.25μm; x B y C z The gradient transition layer has a columnar structure, Cr x B y C z The thickness of the gradient transition layer is 0.05 μm to 0.10 μm; the B-DLC functional layer has a dense featureless structure, and the thickness of the B-DLC functional layer is 0.8 μm to 2.0 μm;

[0008] In the Cr base layer, the mass percentage of Cr is 99.5% to 99.99%; x By C z In the gradient transition layer, the mass percentage of Cr is greater than 0 and does not exceed 99.99%, the mass percentage of B is greater than 0 and does not exceed 8%, and the balance is C; in the B-DLC functional layer, the mass percentage of B is 3% to 5%, and the balance is C.

[0009] In an optional embodiment, along the direction from close to the Cr primer layer to away from the Cr primer layer, Cr x B y C z In the gradient transition layer, the mass percentage of Cr gradually decreases from 99.99% to 0, and the mass percentage of B gradually increases from 0 to 8%.

[0010] In an optional embodiment, the high temperature wear-resistant self-lubricating boron-doped diamond-like coating has at least one of the following characteristics:

[0011] Feature 1: The hardness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is H, and the range of H is 20.0GPa to 25.0GPa; preferably 20.5GPa to 24.7GPa;

[0012] Feature 2: The equivalent elastic modulus of the high-temperature wear-resistant self-lubricating boron-doped diamond-like carbon coating is E*, and the range of E* is 185 GPa to 245 GPa, preferably 189.5 GPa to 242.2 GPa;

[0013] Feature 3: H / E* of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is ≥ 0.1; preferably 0.102 to 0.108;

[0014] Feature 4: The friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C is 0.090 to 0.100, preferably 0.090 to 0.098;

[0015] Feature 5: The friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is 0.050-0.055 in an atmospheric environment at 400°C;

[0016] Feature 6: The friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is 0.040-0.050 in an atmospheric environment at 500°C;

[0017] Feature 7: The wear rate of high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C does not exceed 3.50×10 -7 m 3 / N·m;

[0018] Feature 8: The wear rate of high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in 400°C atmospheric environment does not exceed 1.50×10 -6 m 3 / N·m;

[0019] Feature 9: The wear rate of high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in 500°C atmospheric environment does not exceed 5.0×10 -6 m 3 / N·m;

[0020] Feature 10: The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating can form an easily lubricated lamellar amorphous carbon transfer film rich in boron oxide in situ at the wear scar when rubbed at 400℃~500℃.

[0021] In a second aspect, the present invention provides a method for preparing a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating as described in any one of the aforementioned embodiments, comprising the following steps: depositing a Cr base layer, a Cr base layer, and a Cr base layer on the surface of a substrate in sequence; x B y C z Gradient transition layer and B-DLC functional layer.

[0022] In an optional embodiment, the Cr base layer is prepared by DC magnetron sputtering;

[0023] The preparation conditions of the Cr base layer include: the vacuum degree in the equipment chamber is better than 1.0×10 -3 Pa, 120sccm~150sccm of argon gas is introduced into the equipment, and the gas pressure is maintained at 0.40Pa~0.45Pa; the substrate bias is -200V to -250V, and the bias duty cycle is 50%~60%; the target current is 1.0A~2.0A, and the deposition time is 5min~10min; the target material is a metal chromium target, of which the Cr content accounts for 99.5wt%~99.99wt%.

[0024] In an optional embodiment, Cr is prepared by DC magnetron sputtering. x B y C z Gradient transition layer;

[0025] Cr x B y C z The preparation conditions of the gradient transition layer include: introducing 120sccm to 150sccm of argon gas into the equipment, maintaining the gas pressure at 0.40Pa to 0.45Pa; the substrate bias voltage is -200V to -250V, and the bias duty cycle is 50 to 60%; the target materials are metal chromium target and graphite-boron carbide composite target; the current of the metal chromium target gradually decreases from 2.0A to 0A, and the current of the graphite-boron carbide composite target gradually increases from 0A to 2.0A, and the deposition time is 8min to 12min.

[0026] In an optional embodiment, the B-DLC functional layer is prepared by high-power pulsed magnetron sputtering technology assisted by an anode layer ion source;

[0027] The preparation conditions of the B-DLC functional layer include: introducing 80sccm~100sccm argon gas with a gas pressure of 0.25Pa~0.30Pa; the substrate bias is -100V to -150V, and the bias duty cycle is 50%~60%; using a graphite-boron carbide composite target, in which the B content is 5wt%~10wt%; the HiPIMS pulse power is 2.0kW~4.0kW, and the duty cycle is 1.0%~3.0%; the anode layer ion source power is 0.18kW~0.36kW, and the duty cycle is 50%~60%; the deposition time is 4h~6h.

[0028] In an optional embodiment, before preparing the Cr base layer, the substrate is also pre-treated.

[0029] In an optional embodiment, the pretreatment includes grinding and polishing the substrate, then performing ultrasonic cleaning, placing the obtained substrate on a turntable in a vacuum chamber, and finally performing plasma glow cleaning using an anode layer ion source.

[0030] In an optional embodiment, the ultrasonic cleaning time is 40 min to 50 min;

[0031] And / or, plasma glow cleaning includes: fixing the substrate on a vacuum chamber turret, and waiting for the vacuum degree to be better than 1.0×10 -3 Pa, introduce 150sccm~200sccm argon, maintain the gas pressure at 0.60Pa~0.80Pa; at the same time, adjust the substrate bias to -900V to -1000V, and the bias duty cycle is 50%~60%; then turn on the anode layer ion source, the anode layer ion source power is 0.18kW~0.36kW, the duty cycle is 50%~60%, and the plasma glow cleaning time is 10min~15min.

[0032] In a third aspect, the present invention provides an application of a high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating as described in any of the aforementioned embodiments. For example, the high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating can be used to prepare cutting tools, molds, high-tech equipment and their key components.

[0033] In an alternative embodiment, the tool comprises a milling cutter or a micro drill bit moving at high speed.

[0034] In alternative embodiments, the die comprises a stamping die, a punch, or an ejector pin surface.

[0035] In an optional embodiment, the key components include planetary gears, sun gears or internal gear rings.

[0036] The beneficial effects of the present invention include:

[0037] The present invention deposits a Cr base layer and a Cr layer with a specific thickness, structure and element content on the substrate surface. x B y C z The gradient transition layer and the B-DLC functional layer can obtain a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, which has high hardness, high toughness and low friction properties. Especially in a high-temperature atmospheric environment of 400-500°C, the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating exhibits excellent self-lubrication and wear resistance, and can significantly improve the lubrication and wear resistance of the diamond-like film under high-temperature atmospheric conditions.

[0038] This method for preparing a high-temperature, wear-resistant, self-lubricating, boron-doped diamond-like coating offers advantages such as low deposition temperature, high material utilization, good coating uniformity, excellent repeatability, and wide applicability. The resulting high-temperature, wear-resistant, self-lubricating, boron-doped diamond-like coating can be widely used in high-temperature friction and wear protection for cutting tools, molds, high-tech equipment, and their key components, significantly expanding the application range of diamond-like coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0040] Figure 1 This is a scanning electron microscope photograph of the cross-sectional morphology of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating prepared in Example 1;

[0041] Figure 2 The friction coefficient curves and average friction coefficient values of the high-temperature wear-resistant self-lubricating boron-doped diamond-like carbon coating prepared in Example 1 at room temperature (25°C), 400°C and 500°C high-temperature atmospheres;

[0042] Figure 3 The wear scar morphology and transfer film of the high-temperature wear-resistant self-lubricating boron-doped diamond-like carbon coating prepared in Example 1 after friction at room temperature (25°C), 400°C and 500°C high-temperature atmosphere. DETAILED DESCRIPTION

[0043] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0044] The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating provided by the present invention and its preparation method and application are described in detail below.

[0045] The present invention provides a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, which comprises a Cr base layer, a Cr x B y C z Gradient transition layer and B-DLC functional layer.

[0046] The substrate may illustratively but not limitatively include 304 stainless steel, YG6 hard alloy steel, etc.

[0047] The Cr primer layer has a columnar structure, which can be clearly observed.

[0048] The thickness of the Cr primer layer is 0.15 μm to 0.25 μm, such as 0.15 μm, 0.18 μm, 0.20 μm, 0.22 μm or 0.25 μm, etc. It can also be other values within the range of 0.15 μm to 0.25 μm or other ranges.

[0049] If the Cr base layer is thin, it is not conducive to the Cr x B y C z Good adhesion is formed between the gradient transition layer and the substrate; if the Cr base layer is thicker, it is not conducive to the Cr x B y C z The performance of the gradient transition layer.

[0050] In the Cr base layer, the mass percentage of Cr is 99.50% to 99.99%, such as 99.50%, 99.55%, 99.60%, 99.65%, 99.70%, 99.75%, 99.80%, 99.85%, 99.90%, 99.95 or 99.99%, etc., and can also be other values within the range of 99.50% to 99.99% or other ranges.

[0051] If the mass percentage of Cr in the Cr base layer is lower than 99.50%, it will be detrimental to the matrix and Cr x B y C zThe combination between the gradient transition layers causes the coating to easily fall off or crack.

[0052] Cr x B y C z The gradient transition layer has a columnar structure, which can be clearly observed.

[0053] The Cr x B y C z The thickness of the gradient transition layer is 0.05 μm to 0.10 μm, such as 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm or 0.10 μm, etc. It can also be other values within the range of 0.05 μm to 0.10 μm or other ranges.

[0054] If Cr x B y C z The gradient transition layer is too thin, which is not conducive to forming good adhesion between the B-DLC functional layer and the Cr base layer; if the Cr x B y C z The gradient transition layer is relatively thick, which is not conducive to the performance of the B-DLC functional layer.

[0055] The Cr x B y C z In the gradient transition layer, the mass percentage of Cr is greater than 0 and does not exceed 99.99% (such as 0.5%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 99.99%). The mass percentage of B is greater than 0 and does not exceed 8% (such as 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8%), and the balance is C.

[0056] From the direction close to the Cr base layer to the direction away from the Cr base layer, Cr x B y C z In the gradient transition layer, the mass percentage of Cr gradually decreases from 99.99% to 0, and the mass percentage of B gradually increases from 0 to 8%.

[0057] If Cr x B y C z The mass percentage of B in the gradient transition layer exceeds 8%, which is not conducive to the x B y C z Combination between gradient transition layer and B-DLC functional layer.

[0058] The B-DLC functional layer has a dense featureless structure, where “dense” is understood to mean a porosity of no more than 1%.

[0059] The thickness of the B-DLC functional layer is 1.0 μm to 2.0 μm, such as 1.0 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm or 2.0 μm, etc. It can also be any other value within the range of 1.0 μm to 2.0 μm or other ranges.

[0060] If the thickness of the B-DLC functional layer is too thin, it is not conducive to the performance of the B-DLC functional layer; if the thickness of the B-DLC functional layer is too thick, the preparation cost of the coating is increased.

[0061] In the B-DLC functional layer, the mass percentage of B is 3% to 5% (e.g., 3%, 3.5%, 4%, 4.5% or 5%), and the balance is C. That is, the mass percentage of C in the B-DLC functional layer is 95% to 97% (e.g., 95%, 95.5%, 96%, 96.5% or 97%).

[0062] If the mass percentage of B in the B-DLC functional layer is lower than 3%, it is not conducive to the formation of sufficient boron-rich oxide with lubrication and wear reduction properties in the film during the friction process; if the mass percentage of B in the B-DLC functional layer is higher than 5%, it is easy to cause a large amount of hard B4C phase to form in the film, thereby reducing its lubricity.

[0063] In some optional embodiments, the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating has a hardness of H, which ranges from 20.0 GPa to 25.0 GPa. In some preferred embodiments, H is 20.5 GPa to 24.7 GPa, such as 20.5 GPa, 20.6 GPa, 21.1 GPa, 21.4 GPa, 21.6 GPa, 21.9 GPa, 22.1 GPa, 22.5 GPa, 22.6 GPa, 22.9 GPa, 23.6 GPa, 24.2 GPa, or 24.7 GPa, and may also be other values within the range of 20.5 GPa to 24.7 GPa or other ranges.

[0064] In some optional embodiments, the equivalent elastic modulus of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating is E*, and the range of E* is 185GPa to 245GPa. In some preferred embodiments, E* is 189.5GPa to 242.2GPa, such as 189.5GPa, 192.5GPa, 193.4GPa, 197.2GPa, 201.9GPa, 203.8GPa, 206.7GPa, 210.5GPa, 213.8GPa, 214.3GPa, 217.3GPa, 218.1GPa, 224.1GPa, 226.9GPa, 235.0GPa or 242.2GPa, etc., and can also be other values or other ranges within the range of 189.5GPa to 242.2GPa. The above E*=E / (1-ν 2 ), where E is the elastic modulus and ν is the Poisson's ratio.

[0065] In some optional embodiments, the high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating has an H / E* ratio of ≥ 0.1. In some preferred embodiments, H / E* is 0.102 to 0.108, such as 0.102, 0.103, 0.104, 0.105, 0.106, 0.107, or 0.108, or may be other values within the range of 0.102 to 0.108 or other ranges.

[0066] In some optional embodiments, the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C is 0.090-0.100. In some preferred embodiments, the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C is 0.090-0.098, such as 0.090, 0.091, 0.092, 0.093, 0.094, 0.096, 0.097 or 0.098, etc., and may also be other values within the range of 0.090-0.098 or other ranges.

[0067] In some optional embodiments, the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 400°C is 0.050-0.055, such as 0.050, 0.051, 0.052, 0.053, 0.054 or 0.055, etc., and can also be other values within the range of 0.050-0.055 or other ranges.

[0068] In some optional embodiments, the friction coefficient of the above-mentioned high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 500°C is 0.040-0.050, such as 0.040, 0.042, 0.043, 0.044, 0.046, 0.047, 0.049 or 0.050, etc., and can also be other values within the range of 0.040-0.050 or other ranges.

[0069] In some optional embodiments, the wear rate of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment at 25°C does not exceed 3.50×10 -7 m 3 / N·m. In some preferred embodiments, the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment at 25°C is 1.02×10 -7 m 3 / N·m~3.50×10 -7 m 3 / N·m, such as 1.02×10 -7 m 3 / N·m、1.88×10 -7 m 3 / N·m、1.24×10 -7 m 3 / N·m, 2.06×10 -7 m 3 / N·m, 2.16×10 - 7 m 3 / N·m, 2.18×10 -7 m 3 / N·m, 2.24×10 -7 m 3 / N·m, 2.33×10 -7 m 3 / N·m, 2.34×10 -7 m 3 / N·m, 2.35×10 -7 m 3 / N·m, 2.45×10 -7 m 3 / N·m, 2.67×10 -7 m 3 / N·m、3.22×10 -7 m 3 / N·m、3.41×10 - 7 m 3 / N·m or 3.50×10 -7 m 3 / N·m, etc., or 1.02×10 -7m 3 / N·m~3.50×10 -7 m 3 / N·m or other ranges.

[0070] In some optional embodiments, the wear rate of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment at 400°C is no more than 1.50×10 -6 m 3 In some preferred embodiments, the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment at 400°C can be 1.04×10 -6 m 3 / N·m~1.50×10 -6 m 3 / N·m, such as 1.04×10 -6 m 3 / N·m、1.08×10 -6 m 3 / N·m、1.16×10 -6 m 3 / N·m、1.19×10 -6 m 3 / N·m、1.21×10 -6 m 3 / N·m、1.22×10 -6 m 3 / N·m、1.23×10 -6 m 3 / N·m, 1.26×10 -6 m 3 / N·m、1.29×10 - 6 m 3 / N·m、1.35×10 -6 m 3 / N·m, 1.37×10 -6 m 3 / N·m、1.42×10 -6 m 3 / N·m、1.47×10 -6 m 3 / N·m or 1.50×10 -6 m 3 / N·m, etc., can also be 1.04×10 -6 m 3 / N·m~1.50×10 -6 m 3 / N·m or other ranges.

[0071] In some optional embodiments, the wear rate of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 500°C does not exceed 5.0×10 -6 m 3 In some preferred embodiments, the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 500°C can be 2.05×10 -6 m 3 / N·m~4.97×10 -6 m 3 / N·m, such as 2.05×10 -6 m 3 / N·m, 2.15×10 -6 m 3 / N·m, 2.33×10 -6 m 3 / N·m, 2.51×10 -6 m 3 / N·m, 2.61×10 -6 m 3 / N·m, 2.61×10 -6 m 3 / N·m, 2.74×10 -6 m 3 / N·m, 2.85×10 -6 m 3 / N·m, 2.94×10 -6 m 3 / N·m、3.29×10 -6 m 3 / N·m、3.35×10 -6 m 3 / N·m、3.45×10 -6 m 3 / N·m、3.51×10 -6 m 3 / N·m or 4.97×10 -6 m 3 / N·m, etc., or 2.05×10 -6 m 3 / N·m~4.97×10 -6 m 3 / N·m or other ranges.

[0072] In the high-temperature, wear-resistant, self-lubricating boron-doped diamond-like carbon coating of this invention, boron doping not only stabilizes the amorphous structure of the DLC coating and effectively inhibits its graphitization tendency, but also promotes the formation of a transfer film, optimizes the lubrication mechanism, and significantly enhances the self-lubricating properties of the DLC coating at higher temperatures. Furthermore, boron doping generates a hard boron carbide phase within the coating, further enhancing its hardness and wear resistance.

[0073] It is important to emphasize that the inventors have creatively discovered that boron doping offers the following advantages over silicon doping: Boron incorporation not only stabilizes the amorphous structure of the DLC coating and reduces its tendency to graphitize, but also positively impacts its lubrication mechanism by promoting the formation of a transfer film, thereby enhancing its self-lubricating properties at high temperatures. Furthermore, boron doping forms a hard boron carbide phase within the coating, further enhancing its hardness and wear resistance.

[0074] In the present invention, a Cr base layer and a Cr layer with a specific thickness, structure and element content are deposited on the surface of the substrate. x B y C z The gradient transition layer and the B-DLC functional layer can obtain a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, which has high hardness, high toughness and low friction properties. Especially in a high-temperature atmospheric environment of 400-500°C, the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating can form an easily lubricated lamellar amorphous carbon transfer film rich in boron oxide in situ at the wear scar, which can effectively reduce the friction coefficient, show excellent self-lubricating and wear-resistant properties, and have excellent lubrication and friction reduction effects at high temperatures.

[0075] Accordingly, the present invention also provides a method for preparing the above-mentioned high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, comprising the following steps: depositing a Cr primer layer, a Cr x B y C z Gradient transition layer and B-DLC functional layer.

[0076] In some optional embodiments, the Cr base layer is prepared by DC magnetron sputtering.

[0077] The preparation conditions of the Cr bottom layer may include: the vacuum degree in the equipment chamber is better than 1.0×10 -3Pa, 120 sccm to 150 sccm (such as 120 sccm, 125 sccm, 130 sccm, 135 sccm, 140 sccm, 145 sccm or 150 sccm, etc.) of argon is introduced into the equipment, and the pressure is maintained at 0.40 Pa to 0.45 Pa (such as 0.40 Pa, 0.41 Pa, 0.42 Pa, 0.43 Pa, 0.44 Pa or 0.45 Pa, etc.); the substrate bias voltage is -20 0V to -250V (such as -200V, -210V, -220V, -230V, -240V or -250V, etc.), the bias duty cycle is 50% to 60% (such as 50%, 55% or 60%, etc.); the target current is 1.0A to 2.0A (such as 1.0A, 1.5A or 2.0A, etc.), and the deposition time is 5min to 10min (such as 5min, 6min, 7min, 8min, 9min or 10min, etc.).

[0078] The target material used in the above-mentioned Cr bottom layer preparation process is a metal chromium target, wherein the mass percentage of Cr is 99.50% to 99.99%.

[0079] In some optional embodiments, Cr is prepared by DC magnetron sputtering. x B y C z Gradient transition layer.

[0080] Cr x B y C z The preparation conditions of the gradient transition layer include: introducing 120 sccm to 150 sccm (such as 120 sccm, 125 sccm, 130 sccm, 135 sccm, 140 sccm, 145 sccm or 150 sccm, etc.) of argon into the equipment, maintaining the gas pressure at 0.40 Pa to 0.45 Pa (such as 0.40 Pa, 0.41 Pa, 0.42 Pa, 0.43 Pa, 0.44 Pa or 0.45 Pa, etc.); the substrate bias is -200 V to -250 V (such as -200 V, -210 V, -220 V, -230 V, -240 V or -250 V, etc.), and the bias duty cycle is 50% to 60% (such as 50%, 55% or 60%, etc.). The target materials used are a metal chromium target and a graphite-boron carbide composite target (C-B4C composite target); the current of the metal chromium target is gradually reduced from 2.0 A to 0 A, and the current of the graphite-boron carbide composite target is gradually increased from 0 A to 2.0 A, and the deposition time is 8 min to 12 min (such as 8 min, 9 min, 10 min, 11 min or 12 min, etc.).

[0081] It should be noted that Cr x B y C zThe metal chromium target and graphite-boron carbide composite target used in the preparation of the gradient transition layer, wherein the metal chromium target is the same as the target material used in the preparation of the Cr base layer, and the graphite-boron carbide composite target is the same as the target material used in the preparation of the B-DLC functional layer.

[0082] In some optional embodiments, the B-DLC functional layer is prepared by using a high-power pulsed magnetron sputtering technology assisted by an anode ion source.

[0083] Preparation conditions of the B-DLC functional layer may include: an argon gas flow rate of 80 sccm to 100 sccm (such as 80 sccm, 85 sccm, 90 sccm, 95 sccm or 100 sccm, etc.), a gas pressure of 0.25 Pa to 0.30 Pa (such as 0.25 Pa, 0.26 Pa, 0.27 Pa, 0.28 Pa, 0.29 Pa or 0.30 Pa, etc.); a substrate bias of -100 V to -150 V (such as -100 V, -110 V, -120 V, -130 V, -140 V or -150 V, etc.), and a bias duty cycle of 50% to 60% (such as 50%, 55% or 60%, etc.). A graphite-boron carbide composite target is used, wherein the B content is 5wt% to 10wt% (such as 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%), the HiPIMS pulse power is 2.0kW to 4.0kW (such as 2.0kW, 2.5kW, 3.0kW, 3.5kW or 4.0kW, etc.), and the duty cycle is 1.0% to 3.0% (such as 1.0%, 1.5%, 2.0%, 2.5kW, etc.). .5% or 3.0%, etc.); the anode layer ion source power is 0.18kW to 0.36kW (such as 0.18kW, 0.21kW, 0.24kW, 0.27kW, 0.30kW, 0.33kW or 0.36kW, etc.), the duty cycle is 50% to 60% (such as 50%, 55% or 60%, etc.); the deposition time is 4h to 6h (such as 4.0h, 4.5h, 5.0h, 5.5h or 6.0h, etc.).

[0084] The high-power pulsed magnetron sputtering deposition technology assisted by the anode layer ion source has an extremely high ionization rate and high bombardment energy, making it easier to prepare a composite lubricating coating with special properties.

[0085] For reference, the equipment used in the high-power pulsed magnetron sputtering deposition technology assisted by the anode layer ion source adopted in this application mainly includes a vacuum chamber, a turntable system, a DC power supply, a high-power pulsed power supply, an anode layer ion source, an air intake unit and a molecular pump, wherein the DC power supply, the anode layer ion source and the high-power pulsed power supply are evenly distributed on the inner wall of the vacuum chamber, and a turntable that can revolve and rotate is provided in the vacuum chamber. The DC power supply is installed on the metal chromium target, the high-power pulsed power supply is installed on the C-B4C composite target, and the substrate is installed on the turntable. Regarding the equipment and deposition principles used for high-power pulsed magnetron sputtering and DC magnetron sputtering deposition assisted by the anode layer ion source, reference can be made to the relevant content of high-power pulsed magnetron sputtering and DC magnetron sputtering, and no excessive restrictions are made here.

[0086] In some embodiments, before preparing the Cr base layer, the substrate is further pre-treated.

[0087] The pretreatment includes grinding and polishing the substrate, then ultrasonic cleaning, and then placing the obtained substrate on a rotating rack in a vacuum chamber and performing plasma glow cleaning using an anode layer ion source.

[0088] Among them, ultrasonic cleaning refers to ultrasonic cleaning in alkaline detergent and deionized water, and the ultrasonic cleaning time can be 40min to 50min, such as 40min, 42min, 45min, 48min or 50min, etc., or other values within the range of 40min to 50min.

[0089] Plasma glow cleaning may include placing the substrate into a vacuum chamber and evacuating the chamber to a vacuum better than 1.0×10 -3 Pa, then introduce 150 sccm to 200 sccm (such as 150 sccm, 160 sccm, 170 sccm, 180 sccm, 190 sccm or 200 sccm, etc.) of argon, and adjust the gas pressure to 0.60 Pa to 0.80 Pa (such as 0.60 Pa, 0.65 Pa, 0.70 Pa, 0.75 Pa or 0.80 Pa, etc.); at the same time, adjust the substrate bias to -900 V to -1000 V (such as -900 V, -950 V or -1000 V, etc.), and the bias duty cycle is 50% to 60% (such as 50%, 55% or 60%, etc.); then turn on the anode layer ion source, the anode layer ion source power is 0.18kW~0.36kW (such as 0.18kW, 0.21kW, 0.24kW, 0.27kW, 0.30kW, 0.33kW or 0.36kW, etc.), the duty cycle is 50%~60% (such as 50%, 55% or 60%, etc.), and the plasma glow cleaning time is 10min~15min (such as 10min, 11min, 12min, 13min, 14min or 15min, etc.).

[0090] In the present invention, the high temperature wear-resistant self-lubricating boron-doped diamond-like coating provided by the present invention significantly changes the microstructure and properties of the DLC coating and improves its hardness and wear resistance. In the process of realizing this design, DC magnetron sputtering is used to deposit Cr base layer and Cr x B y C z A gradient transition layer is deposited, and a high-power pulsed magnetron sputtering system assisted by an anode layer ion source is used to deposit the functional layer. High-power pulsed magnetron sputtering technology generates high-energy plasma and significantly increases the ionization rate of the sputtering gas through ion source assistance, thereby enhancing the bombardment energy during the deposition process. This series of optimizations not only improves the quality of the film, but also significantly enhances key properties such as toughness, wear resistance, and adhesion. Compared with traditional magnetron sputtering equipment, high-power pulsed magnetron sputtering technology assisted by an anode layer ion source can more easily produce composite lubricating coatings with specialized properties.

[0091] Through the specific preparation method and preparation conditions provided by the present invention, a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating with high hardness, high toughness and low friction performance is effectively prepared.

[0092] In addition, the present invention also provides an application of the above-mentioned high-temperature wear-resistant self-lubricating boron-doped diamond-like coating. For example, the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating can be used to prepare cutting tools, molds, high-tech equipment and their key components.

[0093] The cutting tool may exemplarily include a high-speed milling cutter or a micro-drill bit, etc. The mold may exemplarily include a stamping die, a punch, or an ejector pin surface, etc. The key components may exemplarily include a planetary gear, a sun gear, or an internal gear ring, etc.

[0094] The high-strength, tough, wear-resistant, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating provided by the present invention and its preparation method and application are described in detail below.

[0095] Example 1

[0096] This embodiment provides a high-strength, high-toughness, wear-resistant, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating, which is prepared by the following method:

[0097] S1: substrate pretreatment.

[0098] A 304 stainless steel substrate was ultrasonically cleaned for 45 minutes using an alkaline detergent and then deionized water. The dried substrate was then mounted on a rotating rack. Evacuation was then performed to a base vacuum of better than 1.0 × 10-3 Pa. Argon gas was introduced at 180 sccm and the pressure was adjusted to 0.72 Pa. The substrate bias voltage was adjusted to -1000 V with a duty cycle of 60%. The anode layer ion source was activated with a power of 0.25 kW and a duty cycle of 60%, and the substrate was plasma-glow cleaned for 15 minutes.

[0099] S2: preparing a Cr base layer on the substrate surface.

[0100] After plasma glow cleaning, 120 sccm of argon was introduced into the equipment, maintaining a pressure of 0.40 Pa. The substrate bias voltage was -250 V with a 60% duty cycle. The target current was 2.0 A, and the deposition time was 5 minutes, forming a Cr base layer. The target material was a metallic chromium target with a Cr content of 99.80 wt%.

[0101] S3: Prepare Cr on the surface of Cr base layer x B y C z Gradient transition layer.

[0102] After the Cr base deposition was completed, 120 sccm of argon was continued to be introduced to maintain the gas pressure at 0.40 Pa; the substrate bias voltage was -250 V, and the bias duty cycle was 60%; the targets used were metal chromium target and graphite-boron carbide (C-B4C) composite target; the current of the metal chromium target was gradually reduced from 2.0 A to 0 A, and the current of the C-B4C mosaic composite target was gradually increased from 0 A to 2.0 A, and the deposition time was 10 min to form Cr. x B y C z Gradient transition layer.

[0103] S4: In Cr x B y C z A B-DLC functional layer is prepared on the surface of the gradient transition layer.

[0104] Cr x B y C zAfter the gradient transition layer is deposited, 90 sccm of argon gas is introduced at a pressure of 0.28 Pa. The substrate bias voltage is -125 V with a bias duty cycle of 60%. A graphite-boron carbide (C-B4C) composite target with an 8wt% B content is used. The HiPIMS pulse power is 3.0 kW with a duty cycle of 1.0%. The anode layer ion source assists in ionizing the sputtering gas at an anode layer ion source power of 0.25 kW and a duty cycle of 60%. The deposition time is 4 hours, forming the B-DLC functional layer. The rotor speed is maintained at a stable 2 rpm throughout the deposition process, and the material is allowed to cool naturally after the deposition is completed.

[0105] Figure 1 This is a scanning electron microscope photo of the cross section of the coating sample prepared in this embodiment, from bottom to top: 304 stainless steel substrate, Cr base layer, Cr x B y C z Gradient transition layer and B-DLC functional layer. From this figure, it can be seen that the B-DLC functional layer can x B y C z The gradient transition layer grows well, Cr x B y C z The gradient transition layer can grow well on the Cr base layer. x B y C z The gradient transition layer exhibits a distinct columnar structure, and the B-DLC functional layer presents a dense featureless structure.

[0106] After testing, the total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.04 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, and the thickness of the B-DLC functional layer is 0.84 μm. The mass percentage of Cr in the Cr base layer is 99.80%. x B y C z In the gradient transition layer, the mass percentage of Cr is 0-99.99%, the mass percentage of B is 0-8%, and the remainder is C (in the direction from close to the Cr base layer to far away from the Cr base layer, Cr x B y C z In the gradient transition layer, the mass percentage of Cr gradually decreases, and the mass percentage of B gradually increases. In the B-DLC functional layer, the mass percentage of B is 3.36%, and the mass percentage of C is 96.64%.

[0107] Example 2

[0108] The difference between this embodiment and embodiment 1 is that the substrate of this embodiment is YG6 cemented carbide.

[0109] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.04 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, and the thickness of the B-DLC functional layer is 0.84 μm. The mass percentage of Cr in the Cr base layer is 99.80%. x B y C z In the gradient transition layer, the mass percentage of Cr is 0-99.99%, the mass percentage of B is 0-8%, and the balance is C. In the B-DLC functional layer, the mass percentage of B is 3.36%, and the mass percentage of C is 96.64%.

[0110] Example 3

[0111] The difference between this embodiment and embodiment 1 is that the substrate bias voltage during the deposition of the B-DLC functional layer in this embodiment is -100V.

[0112] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.18 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.98 μm, and the mass percentage of B in the B-DLC functional layer is 3.04% and the mass percentage of C is 96.96%.

[0113] The rest are the same as in Example 1.

[0114] Example 4

[0115] The difference between this embodiment and embodiment 1 is that the substrate bias voltage during the deposition of the B-DLC functional layer in this embodiment is -150V.

[0116] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.10 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.90 μm, and the mass percentage of B in the B-DLC functional layer is 3.14% and the mass percentage of C is 96.86%.

[0117] The rest are the same as in Example 1.

[0118] Example 5

[0119] The difference between this embodiment and embodiment 1 is that in this embodiment, 80 sccm of argon gas is introduced during the deposition of the B-DLC functional layer, and the gas pressure is adjusted to 0.25 Pa.

[0120] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.02 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.82 μm, and the mass percentage of B in the B-DLC functional layer is 3.08% and the mass percentage of C is 96.92%.

[0121] The rest are the same as in Example 1.

[0122] Example 6

[0123] The difference between this embodiment and embodiment 1 is that in this embodiment, 100 sccm of argon gas is introduced during the deposition of the B-DLC functional layer, and the gas pressure is adjusted to 0.30 Pa.

[0124] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.17 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.97 μm, and the mass percentage of B in the B-DLC functional layer is 3.91% and the mass percentage of C is 96.09%.

[0125] The rest are the same as in Example 1.

[0126] Example 7

[0127] The difference between this embodiment and embodiment 1 is that the deposition time of the B-DLC functional layer in this embodiment is 6 hours.

[0128] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.43 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.23 μm, and the mass percentage of B in the B-DLC functional layer is 3.38% and the mass percentage of C is 96.62%.

[0129] The rest are the same as in Example 1.

[0130] Example 8

[0131] The difference between this embodiment and embodiment 1 is that the HiPIMS pulse power during the deposition of the B-DLC functional layer in this embodiment is 4.0 kW.

[0132] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.46 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.26 μm, and the mass percentage of B in the B-DLC functional layer is 3.71% and the mass percentage of C is 96.29%.

[0133] The rest are the same as in Example 1.

[0134] Example 9

[0135] This embodiment is similar to the embodiment 1 except that the power of the anode layer ion source in this embodiment is 0.18 kW.

[0136] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.47 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.27 μm, and the mass percentage of B in the B-DLC functional layer is 3.25% and the mass percentage of C is 96.75%.

[0137] The rest are the same as in Example 1.

[0138] Example 10

[0139] The difference between this embodiment and embodiment 1 is that the power of the anode layer ion source in this embodiment is 0.36 kW.

[0140] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.02 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.82 μm, and the mass percentage of B in the B-DLC functional layer is 3.65% and the mass percentage of C is 96.35%.

[0141] The rest are the same as in Example 1.

[0142] Example 11

[0143] The difference between this embodiment and Example 1 is that: in this embodiment, 80 sccm of argon gas is introduced when depositing the B-DLC functional layer, and the gas pressure is 0.25 Pa; the substrate bias is -150 V, and the bias duty cycle is 60%; a graphite-boron carbide (C-B4C) composite target is used, the B content is 8wt%, the HiPIMS pulse power is 2.0kW, and the duty cycle is 1.0%; the anode layer ion source is used to assist in the ionization of the sputtering gas, and the corresponding anode layer ion source power is 0.36kW; the deposition time is 4h.

[0144] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 1.00 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.80 μm, and the mass percentage of B in the B-DLC functional layer is 3.36% and the mass percentage of C is 96.64%.

[0145] The rest are the same as in Example 1.

[0146] Example 12

[0147] The difference between this embodiment and Example 1 is that: in this embodiment, 100 sccm of argon gas is introduced when depositing the B-DLC functional layer, and the gas pressure is 0.30 Pa; the substrate bias is -100 V, and the bias duty cycle is 60%; a graphite-boron carbide (C-B4C) composite target is used, and the B content is 8 wt%; the HiPIMS pulse power is 4.0 kW, and the duty cycle is 1.0%; the anode layer ion source power is 0.18 kW, and the duty cycle is 60%; and the deposition time is 6 h.

[0148] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 2.20 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 2.00 μm, and the mass percentage of B in the B-DLC functional layer is 3.36% and the mass percentage of C is 96.64%.

[0149] The rest are the same as in Example 1.

[0150] Example 13

[0151] This embodiment provides a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, which is prepared by the following method:

[0152] S1: substrate pretreatment.

[0153] The 304 stainless steel substrate was ultrasonically cleaned with alkaline detergent and deionized water for 45 minutes, and then the dried substrate was mounted on a rotating rack. The vacuum was then evacuated, and the background vacuum was better than 1.0×10 -3 Pa; introduce 200 sccm argon and adjust the gas pressure to 0.80 Pa; adjust the substrate bias to -1000 V and the duty cycle to 60%; turn on the anode layer ion source, set the power to 0.36 kW and the duty cycle to 60%, and perform plasma glow cleaning on the substrate for 15 minutes.

[0154] S2: preparing a Cr base layer on the substrate surface.

[0155] After plasma glow cleaning, 150 sccm of argon gas was introduced into the device to maintain the gas pressure at 0.45 Pa; the substrate bias voltage was -200 V, the bias duty cycle was 50%; the target current was 1.0 A, and the deposition time was 10 minutes to form a Cr base layer.

[0156] S3: Prepare Cr on the surface of Cr base layer x B y C z Gradient transition layer.

[0157] After the Cr base deposition is completed, 150 sccm of argon gas is continued to be introduced to maintain the gas pressure at 0.45 Pa; the substrate bias voltage is -200 V, and the bias duty cycle is 50%; the targets are metal chromium target and graphite-boron carbide (C-B4C) composite target; the current of the metal chromium target is gradually reduced from 2.0 A to 0 A, and the current of the C-B4C mosaic composite target is gradually increased from 0 A to 2.0 A, and the deposition time is 10 min to form Cr. x B y C z Gradient transition layer.

[0158] S4: In Cr x B y C z A B-DLC functional layer is prepared on the surface of the gradient transition layer.

[0159] Cr x B y C zAfter the gradient transition layer is deposited, 100 sccm of argon gas is introduced at a pressure of 0.30 Pa. The substrate bias voltage is -150 V with a bias duty cycle of 50%. A graphite-boron carbide (C-B4C) composite target with a B content of 5wt% is used. The HiPIMS pulse power is 3.0 kW with a duty cycle of 3.0%. The anode layer ion source assists in ionizing the sputtering gas with a corresponding anode layer ion source power of 0.36 kW and a duty cycle of 50%. The deposition time is 6 hours, forming the B-DLC functional layer. The rotor speed is maintained at a stable 2 rpm throughout the deposition process, and the material is allowed to cool naturally after the deposition is completed.

[0160] After testing, the total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 2.16 μm, of which the thickness of the Cr base layer is 0.25 μm, and the thickness of the Cr base layer is 0.25 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.86 μm, and the mass percentage of B in the B-DLC functional layer is 3.00% and the mass percentage of C is 97.00%.

[0161] Example 14

[0162] This embodiment provides a high-strength, high-toughness, wear-resistant, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating, which is prepared by the following method:

[0163] S1: substrate pretreatment.

[0164] A 5mm thick 304 stainless steel substrate was ultrasonically cleaned with alkaline detergent and deionized water for 45 minutes, and then the dried substrate was mounted on a rotating rack. The vacuum was then evacuated, and the background vacuum was better than 1.0×10 -3 Pa; introduce 200 sccm argon and adjust the gas pressure to 0.80 Pa; adjust the substrate bias to -1000 V and the duty cycle to 60%; turn on the anode layer ion source, set the power to 0.36 kW and the duty cycle to 60%, and perform plasma glow cleaning on the substrate for 15 minutes.

[0165] S2: preparing a Cr base layer on the substrate surface.

[0166] After plasma glow cleaning, 150 sccm of argon gas was introduced into the device to maintain the gas pressure at 0.45 Pa; the substrate bias voltage was -200 V, the bias duty cycle was 50%; the target current was 1.0 A, and the deposition time was 10 minutes to form a Cr base layer.

[0167] S3: Prepare Cr on the surface of Cr base layer x B y C z Gradient transition layer.

[0168] After the Cr base deposition is completed, 150 sccm of argon gas is continued to be introduced to maintain the gas pressure at 0.45 Pa; the substrate bias voltage is -200 V, and the bias duty cycle is 50%; the targets are metal chromium target and graphite-boron carbide (C-B4C) composite target; the current of the metal chromium target is gradually reduced from 2.0 A to 0 A, and the current of the C-B4C mosaic composite target is gradually increased from 0 A to 2.0 A, and the deposition time is 10 min to form Cr. x B y C z Gradient transition layer.

[0169] S4: In Cr x B y C z A B-DLC functional layer is prepared on the surface of the gradient transition layer.

[0170] Cr x B y C z After the gradient transition layer is deposited, 100 sccm of argon gas is introduced at a pressure of 0.30 Pa. The substrate bias voltage is -150 V with a bias duty cycle of 50%. A graphite-boron carbide (C-B4C) composite target with a B content of 10 wt% is used. The HiPIMS pulse power is 3.0 kW with a duty cycle of 1.0%. The anode layer ion source assists in ionizing the sputtering gas at an anode layer ion source power of 0.36 kW and a duty cycle of 50%. The deposition time is 6 hours, forming the B-DLC functional layer. The rotor speed is maintained at 2 rpm throughout the deposition process, and the material is allowed to cool naturally after the deposition is completed.

[0171] After testing, the total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this embodiment is 2.24 μm, of which the thickness of the Cr base layer is 0.25 μm, and the thickness of the Cr base layer is 0.25 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.94 μm, and the mass percentage of B in the B-DLC functional layer is 7.85% and the mass percentage of C is 92.15%.

[0172] Comparative Example 1

[0173] This comparative example differs from Example 1 in that the B-DLC functional layer was deposited by DC magnetron sputtering. The DC magnetron sputtering conditions included: 90 sccm of argon gas maintained at a pressure of 0.28 Pa; a substrate bias voltage of -125 V with a bias duty cycle of 60%; a DC power supply for deposition using a graphite-boron carbide (C-B4C) composite target with a boron content of 8 wt%; a DC target current of 3.0 A and a DC target voltage of 1000 V; an anode layer ion source with an ion power of 0.25 kW and a duty cycle of 60% for auxiliary ionization of the sputtering gas; and a deposition time of 4 hours to form the B-DLC functional layer. The rotating frame rotation speed was maintained at 2 rpm throughout the deposition process, and the material was allowed to cool naturally after the deposition.

[0174] The total thickness of the high-strength, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.16 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.96 μm, and the mass percentage of B in the B-DLC functional layer is 2.95% and the mass percentage of C is 97.05%.

[0175] Comparative Example 2

[0176] The difference between this comparative example and Example 1 is that the Ar flow rate during the preparation of the B-DLC functional layer is 120 sccm and the gas pressure is maintained at 0.35 Pa.

[0177] The total thickness of the high-strength, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.59 μm, of which the thickness of the Cr primer layer is 0.15 μm, and the thickness of the Cr primer layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.39 μm, and the mass percentage of B in the B-DLC functional layer is 2.64% and the mass percentage of C is 97.36%.

[0178] Comparative Example 3

[0179] The difference between this comparative example and Example 1 is that the substrate bias voltage during the preparation of the B-DLC functional layer is 0V.

[0180] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.72 μm, of which the thickness of the Cr primer layer is 0.15 μm, and the thickness of the Cr primer layer is 0.15 μm. x B y C zThe thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.52 μm, and the mass percentage of B in the B-DLC functional layer is 2.50% and the mass percentage of C is 97.50%.

[0181] Comparative Example 4

[0182] The difference between this comparative example and Example 1 is that the power of the anode layer ion source during the preparation of the B-DLC functional layer is 0 W.

[0183] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.43 μm, of which the thickness of the Cr primer layer is 0.15 μm, and the thickness of the Cr primer layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 1.23 μm, and the mass percentage of B in the B-DLC functional layer is 2.42% and the mass percentage of C is 97.58%.

[0184] Comparative Example 5

[0185] The difference between this comparative example and Example 1 is that the power of the anode layer ion source during the preparation of the B-DLC functional layer is 0.5 kW.

[0186] The total thickness of the high-strength, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating of this comparative example is 0.88 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.68 μm, and the mass percentage of B in the B-DLC functional layer is 3.92% and the mass percentage of C is 96.08%.

[0187] Comparative Example 6

[0188] The difference between this comparative example and Example 1 is that no Cr base layer is deposited in this comparative example.

[0189] The total thickness of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating obtained in this comparative example is 0.89 μm, wherein the thickness of the Cr primer layer is 0 μm, and the thickness of the Cr primer layer is 0 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the B-DLC functional layer is 0.84 μm, and the mass percentage of B in the B-DLC functional layer is 3.36% and the mass percentage of C is 96.64%.

[0190] Comparative Example 7

[0191] The difference between this comparative example and Example 1 is that an undoped DLC coating is prepared in this comparative example.

[0192] The total thickness of the high-strength, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.04 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x B y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the DLC functional layer is 0.84 μm, and the mass percentage of B in the B-DLC functional layer is 0% and the mass percentage of C is 100%.

[0193] Comparative Example 8

[0194] The difference between this comparative example and Example 1 is that the silicon-doped diamond-like carbon coating in this comparative example is prepared by the same process.

[0195] The total thickness of the high-strength, high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating obtained in this comparative example is 1.04 μm, of which the thickness of the Cr base layer is 0.15 μm, and the thickness of the Cr base layer is 0.15 μm. x Si y C z The thickness of the gradient transition layer is 0.05 μm, the thickness of the Si-DLC functional layer is 0.84 μm, and the mass percentage of Si in the Si-DLC functional layer is 3.36% and the mass percentage of C is 96.64%.

[0196] Comparative Example 9

[0197] The difference between this comparative example and Example 1 is that the preparation parameter range of the Cr primer layer is adjusted so that the thickness of the Cr primer layer is 0.10 μm.

[0198] Comparative Example 10

[0199] The difference between this comparative example and Example 1 is that the preparation parameter range of the Cr primer layer is adjusted so that the thickness of the Cr primer layer is 0.40 μm.

[0200] Comparative Example 11

[0201] The difference between this comparative example and Example 1 is that the preparation parameter range of the B-DLC functional layer is adjusted so that the thickness of the B-DLC functional layer is 0.60 μm.

[0202] Comparative Example 12

[0203] The difference between this comparative example and Example 1 is that the preparation parameter range of the B-DLC functional layer is adjusted so that the thickness of the B-DLC functional layer is 2.5 μm.

[0204] Comparative Example 13

[0205] The difference between this comparative example and Example 1 is that the preparation parameter range of the B-DLC functional layer is adjusted so that the mass percentage of B in the B-DLC functional layer is 8.0% and the mass percentage of C is 92.0%.

[0206] Comparative Example 14

[0207] The difference between this comparative example and Example 1 is that: x B y C z The preparation parameter range of the gradient transition layer makes Cr x B y C z The mass percentage of B in the gradient transition layer is 10%.

[0208] Test example

[0209] ①. The high temperature wear-resistant self-lubricating boron-doped diamond-like coatings prepared in Examples 2 to 14 were subjected to structural tests. The results showed that the B-DLC functional layers in the high temperature wear-resistant self-lubricating boron-doped diamond-like coatings prepared in the above examples all had dense featureless structures. The Cr base layer and the Cr x B y C z The gradient transition layers all show obvious columnar structures.

[0210] ②. A. The high temperature wear-resistant self-lubricating boron-doped diamond-like coating prepared in Example 1 was partially tested for performance. The results are shown in Table 1 and Figure 2 shown. Figure 2 The friction coefficient curves and average friction coefficient values of the high-temperature wear-resistant, self-lubricating boron-doped diamond-like coating prepared in Example 1 under different temperature atmospheres are shown, where Ee is the area between the loading curve and the unloading curve, indicating the energy dissipated in the coating due to plastic deformation; Ep is the area under the unloading curve, indicating the elastic energy of the deformation. Figure 2 (a) corresponds to the result at room temperature (25°C), (b) corresponds to the result at 400°C, and (c) corresponds to the result at 500°C.

[0211] The hardness in Table 1 was measured according to GB / T 33051-2016 Determination of Thickness of Hardened Layer of Surface Hardened Films for Optical Functional Films; the equivalent elastic modulus E* was calculated according to the following formula: E* = E / (1-ν 2 ), where E refers to the elastic modulus and ν refers to the Poisson's ratio; the hardness modulus ratio data are rounded off.

[0212] In addition, the same performance tests were performed on the coatings obtained in Examples 2 to 14 and Comparative Examples 1 to 14, and the results are also shown in Table 1.

[0213] B. Friction tests were conducted on the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating prepared in Example 1 and the Al2O3 friction pair under a room temperature (25°C) atmosphere and a high temperature atmosphere of 400°C and 500°C, respectively. The friction time of the friction tests under the conditions of 25°C, 400°C and 500°C was 900s. The results are shown in FIG. Figure 3 And shown in Table 1. Figure 3 (a) corresponds to the result at 25℃, (b) corresponds to the result at 400℃, and (c) corresponds to the result at 500℃. Figure 3 It can also be seen that an easily lubricated lamellar amorphous carbon transfer film rich in boron oxide is in situ formed at the wear scar, resulting in its excellent lubricating and friction-reducing effect.

[0214] Furthermore, the same performance tests were performed on the coatings obtained in Examples 2 to 14 and Comparative Examples 1 to 14, and the results are also shown in Table 1.

[0215] Table 1 Performance results

[0216]

[0217] As shown in Table 1, the high-temperature, wear-resistant, self-lubricating boron-doped diamond-like carbon coating provided by the present invention exhibits high hardness, high toughness, and low friction. The coating exhibits excellent self-lubrication and wear resistance over a wide temperature range from room temperature (25°C) to 500°C, particularly in high-temperature atmospheric environments of 400-500°C.

[0218] In summary, the solution provided by the present invention has at least the following advantages:

[0219] (1) The high-temperature wear-resistant, self-lubricating, boron-doped diamond-like coating provided by the present invention has high hardness, high toughness, and low friction properties. Compared with traditional DLC coatings, the high-temperature wear-resistant, self-lubricating, boron-doped diamond-like coating provided by the present invention can effectively resist external wear and impact.

[0220] (2) The high-temperature, wear-resistant, self-lubricating boron-doped diamond-like carbon coating provided by the present invention exhibits excellent self-lubrication and wear resistance over a wide temperature range from room temperature (25°C) to 500°C, significantly improving the lubrication performance of DLC coatings in high-temperature atmospheres. In particular, in high-temperature atmospheric environments of 400-500°C, the coating forms an easily lubricated, lamellar, boron-oxide-rich amorphous carbon transfer film in situ at the wear scar during friction, effectively reducing the coefficient of friction.

[0221] (3) In terms of preparation method, the present invention innovatively combines DC magnetron sputtering technology with high-power pulse deposition technology assisted by an anode layer ion source. Compared with the traditional magnetron sputtering equipment in existing industrial production, the use of an ion source-assisted high-power pulse magnetron sputtering coating system for preparation increases the bombardment energy during the thin film deposition process, making it easier to prepare a hard nano-composite lubricating coating with special properties. At the same time, this preparation method has significant advantages such as low deposition temperature, high material utilization, low production cost, good coating uniformity, good preparation repeatability, and wide practicality.

[0222] (4) The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating provided by the present invention can be widely used in the fields of high-temperature friction and wear protection of cutting tools, molds, high-tech equipment and their key components. The wear-resistant self-lubricating coating can be maturely applied in the range of 400 to 500°C to meet the lubrication and wear resistance requirements under harsh working conditions of high temperature atmosphere.

[0223] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A high-temperature wear-resistant self-lubricating boron-doped diamond-like coating, characterized in that: The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating comprises a Cr base layer, a Cr x B y C z Gradient transition layer and B-DLC functional layer; The Cr bottom layer has a columnar structure, and the thickness of the Cr bottom layer is 0.15 μm to 0.25 μm; x B y C z The gradient transition layer has a columnar structure, and the Cr x B y C z The thickness of the gradient transition layer is 0.05 μm to 0.10 μm; the B-DLC functional layer has a dense featureless structure, and the thickness of the B-DLC functional layer is 0.8 μm to 2.0 μm; In the Cr primer layer, the mass percentage of Cr is 99.5% to 99.99%; x B y C z In the gradient transition layer, the mass percentage of Cr is greater than 0 and does not exceed 99.99%, the mass percentage of B is greater than 0 and does not exceed 8%, and the balance is C; in the B-DLC functional layer, the mass percentage of B is 3% to 5%, and the balance is C; Along the direction from close to the Cr base layer to away from the Cr base layer, the Cr x B y C z In the gradient transition layer, the mass percentage of Cr gradually decreases from 99.99% to 0%, and the mass percentage of B gradually increases from 0 to 8%; The B-DLC functional layer is prepared by high-power pulsed magnetron sputtering technology assisted by an anode layer ion source; the preparation conditions of the B-DLC functional layer include: introducing 80 sccm~100 sccm argon gas with a gas pressure of 0.25 Pa~0.30 Pa; a substrate bias voltage of -100 V to -150 V, and a bias duty cycle of 50%~60%; a graphite-boron carbide composite target is used, and the B content in the graphite-boron carbide composite target is 5wt%~10wt%; the HiPIMS pulse power is 2.0 kW~4.0 kW, and the duty cycle is 1.0%~3.0%; the anode layer ion source power is 0.18 kW~0.36 kW, and the duty cycle is 50%~60%; and the deposition time is 4h~6h; The hardness of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating is H , H The range is 20.0GPa~25.0GPa; the equivalent elastic modulus of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating is E* , E* The range of the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C is 0.090~0.100; the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 400°C is 0.050~0.055; the friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 500°C is 0.040~0.050; the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 25°C does not exceed 3.50×10 -7 m 3 / N·m; the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 400°C does not exceed 1.50×10 -6 m 3 / N·m; the wear rate of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating in an atmospheric environment of 500°C does not exceed 5.0×10 -6 m 3 / N·m.

2. The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating according to claim 1, characterized in that: The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating has at least one of the following characteristics: Feature 1: The hardness of the high temperature wear-resistant self-lubricating boron-doped diamond-like coating is H , H The range is 20.5GPa~24.7GPa; Feature 2: The equivalent elastic modulus of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is E* , E* The range is 189.5GPa~242.2GPa; Feature 3: The friction coefficient of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is 0.090-0.098 in an atmospheric environment of 25°C; Feature 4: The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating can form an easily lubricated lamellar amorphous carbon transfer film rich in boron oxide in situ at the wear scar when rubbed at 400°C to 500°C.

3. A method for preparing a high-temperature wear-resistant self-lubricating boron-doped diamond-like coating according to claim 1 or 2, characterized in that: The following steps are involved: Cr base layer, Cr x B y C z Gradient transition layer and B-DLC functional layer.

4. The preparation method according to claim 3, characterized in that The Cr base layer is prepared by DC magnetron sputtering; The preparation conditions of the Cr bottom layer include: the vacuum degree in the equipment chamber is better than 1.0×10 -3 Pa, 120sccm~150sccm of argon gas is introduced into the equipment, and the gas pressure is maintained at 0.40Pa~0.45Pa; the substrate bias is -200V to -250V, and the bias duty cycle is 50%~60%; the target current is 1.0A~2.0A, and the deposition time is 5min~10min; the target material is a metal chromium target, in which the Cr content accounts for 99.5wt%~99.99wt%.

5. The preparation method according to claim 3, characterized in that The Cr x B y C z Gradient transition layer; The Cr x B y C z The preparation conditions of the gradient transition layer include: introducing 120sccm~150sccm of argon gas into the equipment, maintaining the gas pressure at 0.40Pa~0.45Pa; the substrate bias is -200V to -250V, and the bias duty cycle is 50~60%; the target materials are metal chromium target and graphite-boron carbide composite target; the current of the metal chromium target gradually decreases from 2.0A to 0A, and the current of the graphite-boron carbide composite target gradually increases from 0A to 2.0A, and the deposition time is 8min~12min.

6. The preparation method according to any one of claims 3 to 5, characterized in that Before preparing the Cr base layer, the substrate is pre-treated.

7. The preparation method according to claim 6, characterized in that The pretreatment includes grinding and polishing the substrate, then ultrasonic cleaning, placing the obtained substrate on a rotating rack in a vacuum chamber, and finally performing plasma glow cleaning using an anode layer ion source.

8. The preparation method according to claim 6, characterized in that Ultrasonic cleaning time is 40min~50min; And / or, plasma glow cleaning includes: fixing the substrate on a vacuum chamber turret, and waiting for the vacuum degree to be better than 1.0×10 -3 Pa, introduce 150sccm~200sccm argon, maintain the gas pressure at 0.60Pa~0.80Pa; at the same time, adjust the substrate bias to -900V to -1000V, and the bias duty cycle is 50%~60%; then turn on the anode layer ion source, the anode layer ion source power is 0.18kW~0.36kW, the duty cycle is 50%~60%, and the plasma glow cleaning time is 10min~15min.

9. An application of the high-temperature wear-resistant self-lubricating boron-doped diamond-like coating according to claim 1 or 2, characterized in that: The high-temperature wear-resistant self-lubricating boron-doped diamond-like coating is used for preparing cutting tools, molds, planetary gears, sun gears or internal gear rings.

10. The use according to claim 9, characterized in that Cutting tools include milling cutters or micro drill bits.

11. The use according to claim 9, characterized in that The mold includes a stamping mold.

Images