CN115961243A - Preparation method of high-density Ta-C coating - Google Patents
Preparation method of high-density Ta-C coating Download PDFInfo
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Abstract
The invention relates to the field of surface modification of a base material, in particular to a preparation method of a high-density Ta-C coating, which comprises the following steps: s10, cleaning a matrix: exciting working gas by arc electron flow to form plasma, and etching and cleaning the surface of the substrate by the plasma; s20, depositing a metal nitride transition layer: plating a metal nitride transition layer on the surface of the substrate by magnetron sputtering; s30, depositing a diamond-like coating: vacuumizing a working chamber, controlling the temperature of the working chamber to be 100-300 ℃, and introducing a carbon source gas and an inert gas, wherein the flow ratio of the carbon source gas to the inert gas is (4-6): (10-15), applying 100-300V bias voltage to the substrate, starting an ultrasonic vibrator to apply ultrasonic waves, wherein the ultrasonic power of the ultrasonic vibrator is 10-50W, and the deposition time is 10-100 min. The invention effectively improves the density of the Ta-C coating and the bonding force between the coating and the substrate by the scheme.
Description
Technical Field
The invention relates to the field of surface modification of a base material, in particular to a preparation method of a high-density Ta-C coating.
Background
Diamond-like carbon (DLC) coatings are a metastable amorphous carbon film consisting mainly of different contents of sp3, sp2 bonds. Because the diamond has the performances similar to those of diamond, such as high hardness, good wear resistance, high elastic modulus, low friction coefficient and the like, the diamond is replaced in many occasions, and the use cost is reduced. DLC coating is widely used in the industries of aerospace, mechanical manufacturing, electronic medical treatment and the like, especially precision lubrication components, milling cutters, drill bits and cutters and the like, obviously prolongs the service life of products, improves the production efficiency and improves the economic benefit. Diamond-like coatings can be classified into Ta-C coatings (hydrogen-free diamond-like coatings) and hydrogen-containing diamond-like coatings, depending on the sp2 and sp3 content. The content of sp3 bonds of the Ta-C coating is 80-90%, the coating is higher than that of a hydrogenated diamond-like coating, and compared with a hydrogen-free diamond-like coating, the coating has the characteristics of higher hardness, elastic modulus, lubricity, resistivity, chemical inertness and the like, and can effectively reduce the friction coefficient.
The preparation of the diamond-like coating mainly comprises the following steps: physical Vapor Deposition (PVD) mainly including magnetron sputtering, arc ion plating, pulsed laser deposition, etc., and Chemical Vapor Deposition (CVD) including hot-filament chemical vapor deposition, plasma Enhanced Chemical Vapor Deposition (PECVD). The several technologies have certain defects that the magnetron sputtering deposition sputtering rate is low, and the atomic energy is low, so that the coating structure is loose; a large amount of carbon particles are generated in the arc ion plating deposition process; the energy consumption of pulse laser deposition is high, the uniformity of the coating is poor, and the deposition area is small; the hot wire vapor deposition technology has high deposition temperature, and influences the self organization and performance in the base material; the plasma chemical enhanced vapor deposition has low efficiency, low atom ionization rate and loose coating structure.
In the Ta-C coating, an arc ion plating cathode arc source is generally adopted for preparation at present, the basic process is to directly carry out arc discharge by using a graphite target, carbon ions and large particles in the discharge process are simultaneously deposited on a base material to be plated, and a Ta-C layer with certain SP3 content is generated. However, discharge arc spots are converged in the discharge process of the graphite target, the moving speed is low, and an etching pit is deep, so that large particles are generated in the deposition process, and the coating quality is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a Ta-C coating capable of improving the compactness of the coating so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a high-density Ta-C coating comprises the following steps:
s10, cleaning a matrix: exciting working gas by arc electron flow to form plasma, and etching and cleaning the surface of the substrate by the plasma;
s20, depositing a metal nitride transition layer: plating a metal nitride transition layer on the surface of the substrate by magnetron sputtering;
s30, depositing a diamond-like coating: vacuumizing a working chamber, controlling the temperature of the working chamber to be 100-300 ℃, and introducing a carbon source gas and an inert gas, wherein the flow ratio of the carbon source gas to the inert gas is (4-6): (10-15), applying 100V-300V bias voltage to the substrate, starting the ultrasonic vibrator to apply ultrasonic waves, and setting the deposition time to be 10 min-100 min.
Further, the substrate cleaning method comprises the steps of putting the substrate into a working chamber, vacuumizing, starting arc discharge to excite plasma, setting arc current to be 60A-200A, applying negative bias voltage of 200V-800V to the surface of the substrate, and introducing mixed gas of inert gas and reducing gas when the gas pressure in the working chamber is reduced to be less than 0.2 Pa-0.5 Pa, wherein the ratio of the inert gas to the reducing gas is (1-3): (10-15), the working temperature is 200-500 ℃, and the working time is 5-20 min.
Further, the inert gas is argon, and the reducing gas is hydrogen or carbon monoxide.
Further, in step S20, the metal nitride transition layer is a multilayer composite coating, and includes a single-component metal nitride coating and a binary-component metal nitride coating, where the single-component metal nitride coating is located on a side close to the substrate, and a nitrogen content of the binary-component metal nitride coating is greater than a nitrogen content of the single-component metal nitride coating.
Further, the plating of the metal nitride transition layer on the surface of the substrate by magnetron sputtering comprises,
s201, vacuumizing the working chamber, introducing argon, starting a first metal target, adjusting the current of the first metal target to be 50-200A, applying 40-300V bias voltage to the substrate, and depositing to form a metal priming layer;
s202, introducing nitrogen, increasing the pressure to 400-500 sccm in a gradient increasing mode, adjusting the pressure of the working chamber to 1-10 pa, and the deposition time to 3-20 min, and stably depositing to form the unitary metal nitride coating;
s203, starting a second metal target, adjusting the current of the second metal target to be 50-200A, adjusting the nitrogen flow to be 100-500 sccm, applying 100-300V bias voltage to the substrate, adjusting the air pressure of the working chamber to be 1-5 pa, and the deposition time to be 3-20 min, and stably depositing to form the binary metal nitride coating.
Further, the first metal target is an aluminum target, and the second metal target is a titanium target.
Further, increasing the flow rate of nitrogen to 400 sccm-500 sccm in a gradient increasing manner includes introducing nitrogen flow to 180 sccm-200 sccm, so that nitrogen atoms react with the ionized target ions of the first metal target to form a nitride thin film, the nitrogen atoms react with surface metal atoms of the first metal target, and metal nitride is generated on the surface of the first metal target; the flow rate of the nitrogen is increased to 310 sccm-330 sccm, and the nitride film forms a nano composite structure with an amorphous phase wrapped by a crystal; the flow rate of the nitrogen gas is increased to 500sccm, so that the nitrogen content in the nitride thin film is increased, and the crystal grains in the unitary metal nitride coating form fine nanocrystalline particles.
Further, in step S30, the ultrasonic vibrators are uniformly distributed on the outer side of the substrate, the number of the ultrasonic vibrators is at least 6, and the ultrasonic power of the ultrasonic vibrators is 10W to 50W.
Further, the substrate is made of alloy materials, and the metal nitride transition layer and the substrate are the same in metal elements.
Further, in step S30, the carbon source gas is acetylene gas, and the inert gas is argon gas.
Compared with the prior art, the invention has the beneficial effects that:
in the stage of depositing the diamond-like coating, the ultrasonic vibrator is arranged, ultrasonic vibration is applied to the substrate in the deposition process, and the power and the vibration frequency of the vibration head determine the size of the transmitted ultrasonic energy. Ultrasonic waves generated by the ultrasonic vibrator are transmitted to a nucleation layer of Ta-C through the inside of the base body, so that crystal grains of Ta-C are refined in the diamond-like carbon nucleation process, and the nucleation density is improved; meanwhile, crystal grains growing on the upper layer are filled into holes and gaps of the lower layer in a mechanical vibration mode, internal stress is eliminated through grain boundary sliding, the binding force between the Ta-C layer and the matrix is improved, further the density of diamond-like carbon nucleation is improved, and the quality of the coating is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a graph illustrating the gradient-type increasing flow rate of nitrogen gas in step S202 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1-2, a method for preparing a high-density Ta-C coating includes the following steps:
s10, cleaning a matrix: and exciting the working gas by arc electron flow to form plasma, and etching and cleaning the surface of the substrate by the plasma.
Further, the substrate cleaning method specifically comprises the steps of putting the substrate into a working chamber, vacuumizing, starting arc discharge to excite plasma, setting arc current to be 60A-200A, applying 200V-800V negative bias on the surface of the substrate, and introducing mixed gas of inert gas and reducing gas when the gas pressure in the working chamber is reduced to be less than 0.2 Pa-0.5 Pa, wherein the ratio of the inert gas to the reducing gas is (1-3): (10-15), the working temperature is 200-500 ℃, and the working time is 5-20 min.
In this embodiment, the inert gas is argon, and the reducing gas is hydrogen or carbon monoxide.
S20, depositing a metal nitride transition layer: plating a metal nitride transition layer on the surface of the substrate by magnetron sputtering; the metal nitride transition layer is a multilayer composite coating and comprises a unitary metal nitride coating and a binary metal nitride coating, wherein the unitary metal nitride coating is positioned on one side close to the substrate, and the nitrogen content of the binary metal nitride coating is greater than that of the unitary metal nitride coating.
Specifically, the step of plating the metal nitride transition layer on the surface of the substrate through magnetron sputtering comprises the following steps:
s201, vacuumizing the working chamber, introducing argon, starting a first metal target, adjusting the current of the first metal target to be 50-200A, applying 40-300V bias voltage to the substrate, and depositing to form a metal bottom layer.
S202, introducing nitrogen, increasing the pressure to 400-500 sccm in a gradient increasing mode, adjusting the pressure of the working chamber to 1-10 pa, and the deposition time to 3-20 min, and stably depositing to form the mono-metal nitride coating;
the method comprises the following steps of firstly introducing nitrogen gas with the flow rate of 180-200 sccm, reacting nitrogen atoms with ionized target ions of the first metal target to form a nitride thin film, reacting the nitrogen atoms with surface metal atoms of the first metal target, and generating metal nitride on the surface of the first metal target; further, the flow rate of the nitrogen is increased to 310 sccm-330 sccm, and the nitride film forms a nano composite structure with an amorphous phase wrapped by a crystal; and finally, increasing the flow of the nitrogen to 500sccm, so that the nitrogen content in the nitride film is increased, and the crystal grains in the metal nitride coating form fine nano-crystal particles.
S203, starting a second metal target, adjusting the current of the second metal target to be 50-200A, adjusting the nitrogen flow to be 100-500 sccm, applying 100-300V bias voltage to the substrate, adjusting the air pressure of the working chamber to be 1-5 pa, and the deposition time to be 3-20 min, and stably depositing to form the binary metal nitride coating.
In this embodiment, the first metal target is an aluminum target, and the second metal target is a titanium target.
S30, depositing a diamond-like coating: vacuumizing a working chamber, controlling the temperature of the working chamber to be 100-300 ℃, and introducing a carbon source gas and an inert gas, wherein the flow ratio of the carbon source gas to the inert gas is (4-6): (10-15), applying 100V-300V bias voltage to the substrate, starting an ultrasonic vibrator to apply ultrasonic waves, wherein the ultrasonic power of the ultrasonic vibrator is 10W-50W, and the deposition time is 10 min-100 min.
In this embodiment, the substrate is clamped on a clamping device, the ultrasonic vibrators are uniformly distributed on the clamping device, and the number of the ultrasonic vibrators is at least 6. Specifically, the scheme is suitable for the clamping device of the arc ion plating method, wherein the clamping device waits for plating of workpieces, such as a milling cutter, a drill bit and a punch, the end face of each ultrasonic vibrator is attached to the back of the clamping device, and each ultrasonic vibrator is uniformly distributed on the back of a supporting plate of the clamping device. During the stage of depositing the diamond-like coating, the ultrasonic energy of the ultrasonic vibrator during working reaches the surface of the substrate for depositing the diamond-like coating through the clamping device.
Further, in step S30, the carbon source gas is acetylene gas, and the inert gas is argon gas. Acetylene gas is used as a carbon source to replace the traditional graphite target in the deposition process, so that the problem of particle pollution in the conventional arc graphite target is solved, and complicated filtering equipment is not needed, so that the equipment is simple in structure and easy to operate. Meanwhile, the electric arc is highly ionized to acetylene gas, so that the coating has good adhesive force and higher hardness.
In this embodiment, the substrate is made of an alloy material, and the metal nitride transition layer and the substrate have the same metal element.
Example (b):
the working chamber is a vacuum chamber
The substrate is aluminum alloy;
the unitary metal nitride is aluminum nitride and titanium nitride, and the binary metal nitride is aluminum titanium nitride;
the first metal target is an aluminum target, and the second metal target is a titanium target;
the inert gas is argon, the reducing gas is hydrogen or carbon monoxide, and the carbon source gas is acetylene gas.
S1: before the coating is deposited, cleaning the substrate to remove the surface oxide film, specifically, fixing the substrate on a coating clamping device in a vacuum chamber, vacuumizing the vacuum chamber, controlling the temperature of the chamber to be 200 ℃, reducing the vacuum degree in the chamber to be below 0.5pa, and introducing mixed gas of argon and carbon monoxide in a ratio of (1-3): (10-15), keeping the air pressure of the chamber at 0.8Pa, starting arc discharge to excite plasma, setting the arc current at 160A, applying a negative bias voltage of 700V to the substrate to be plated, and closing the arc current, wherein the cleaning time is 20min, and the surface cleaning work of the substrate is finished.
And S2, depositing a metal nitride transition layer, namely vacuumizing the vacuum chamber, introducing argon, starting a first metal target, adjusting the current of the first metal target to be 80A, activating the surface of the substrate, applying 80V bias voltage to the surface of the substrate, and depositing to form a metal priming layer with a certain thickness.
Introducing nitrogen in a gradient increasing mode, specifically: and adjusting the air pressure of the cavity to be 0.8pa, the temperature in the cavity to be 350-500 ℃, and the deposition time to be 3-20 min, and stably depositing to form the mono-metal nitride coating. Firstly, introducing nitrogen with the flow rate of 180-200 sccm, wherein when the nitrogen flow is low, nitrogen atoms in a coating cavity react with ionized target ions to generate a nitride film, and simultaneously directly react with metal atoms on the surface of a target to generate metal nitride on the surface of the target; further, the nitrogen flow is increased to 310 sccm-330 sccm, and a nitride thin film coating crystal consisting of face-centered cubic nitride and tetragonal phase nitride grows to have an obvious nano composite structure of which an amorphous phase wraps the crystal; furthermore, the nitrogen flow is slowly increased to 500sccm from 310sccm to 330sccm, so that the nitrogen content in the film is increased, the diameter of the crystal column is reduced, the compactness of the columnar crystal is gradually increased, the crystal grains of the coating are fine nanocrystalline particles, the coating is uniform and compact, the surface is smooth, the surface quality is good, and the bonding force of the coating is better.
And opening a second metal target, adjusting the current of the second metal target to be 50-200A, adjusting the nitrogen flow to be 100-500 sccm, applying 100-300V bias voltage to the substrate, adjusting the air pressure of the working chamber to be 1-5 pa, and the deposition time to be 3-20 min, and stably depositing to form the binary metal nitride coating.
S3, depositing the diamond-like coating, specifically: after the vacuum chamber is vacuumized, controlling the temperature of the chamber at 200 ℃, and introducing mixed gas of argon and acetylene, wherein the flow ratio is (4-6): (10-15), adjusting the partial pressure of argon to be 20pa and the partial pressure of acetylene gas to be 20pa, applying a bias voltage of 120V to the substrate, simultaneously turning on an ultrasonic vibrator, setting the ultrasonic power to be 20W, setting the plating time to be 30 min, and turning off the ultrasonic after the plating is finished.
In this example, the bonding force between the Ta-C coated film and the substrate obtained in the above embodiment was measured by a scratch tester, and the average critical load was as shown in Table I.
TABLE 1
As can be seen from the above table, compared with the conventional coating, the binary nitride-based Ta-C coating prepared in this embodiment significantly improves the bonding force between the film and the substrate, improves the nucleation density and uniformity of the Ta-C coating, effectively reduces the agglomeration of crystal grains, reduces the internal stress of the coating, and further improves the growth rate and surface quality of the film.
The formation mechanism of sp3 bonds in the Ta-C film is generally considered as a subsurface injection model, namely, carbon ions are injected into the subsurface of a substrate under the action of certain energy and can form sp3 bonds under the action of certain compressive stress, and ions with smaller energy can only be attached to the surface and cannot form sp3 bonds. In this example, the SP3 content of the Ta-C film was measured by Raman spectroscopy, and the second table shows the SP3 content in the Ta-C film.
TABLE 2
As can be seen from the second table, the sp3 content of the Ta-C coating formed by ultrasonic vibration and the Al Ti N group is obviously increased compared with that of the traditional coating, the sp3 content of the diamond-like carbon film has larger influence on the hardness, and the hardness of the ultrasonic vibration and the Al Ti N group composite Ta-C coating is measured by a micro Vickers hardness tester to be more than 6000HV, so that the coating quality is greatly improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-density Ta-C coating is characterized by comprising the following steps:
s10, cleaning a matrix: exciting working gas by arc electron flow to form plasma, and etching and cleaning the surface of the substrate by the plasma;
s20, depositing a metal nitride transition layer: plating a metal nitride transition layer on the surface of the substrate by magnetron sputtering;
s30, depositing a diamond-like coating: vacuumizing a working chamber, controlling the temperature of the working chamber to be 100-300 ℃, and introducing a carbon source gas and an inert gas, wherein the flow ratio of the carbon source gas to the inert gas is (4-6): (10-15), applying 100-300V bias voltage to the substrate, starting an ultrasonic vibrator to apply ultrasonic waves, wherein the ultrasonic power of the ultrasonic vibrator is 10-50W, and the deposition time is 10-100 min.
2. The method for preparing a Ta-C coating with high compactness according to claim 1, wherein the cleaning of the substrate comprises placing the substrate in a working chamber, vacuumizing, starting arc discharge to excite plasma, setting an arc current to be 60A-200A, applying a negative bias voltage of 200V-800V on the surface of the substrate, and introducing a mixed gas of an inert gas and a reducing gas when the gas pressure in the working chamber is reduced to be less than 0.2 Pa-0.5 Pa, wherein the ratio of the inert gas to the reducing gas is (1-3): (10-15), the working temperature is 200-500 ℃, and the working time is 5-20 min.
3. The method for preparing a Ta-C coating with high compactness according to claim 2, characterized in that the inert gas is argon gas, and the reducing gas is hydrogen gas or carbon monoxide gas.
4. The method according to claim 1, wherein in step S20, the metal nitride transition layer is a multi-layer composite coating comprising a mono-metal nitride coating and a binary-metal nitride coating, the mono-metal nitride coating is disposed on a side close to the substrate, and the nitrogen content of the binary-metal nitride coating is greater than that of the mono-metal nitride coating.
5. The method for preparing a Ta-C coating with high compactness according to claim 4, wherein the plating of the metal nitride transition layer on the surface of the substrate by magnetron sputtering comprises,
s201, vacuumizing the working chamber, introducing argon, starting a first metal target, adjusting the current of the first metal target to be 50-200A, applying 40-300V bias voltage to the substrate, and depositing to form a metal priming layer;
s202, introducing nitrogen, increasing the pressure to 400-500 sccm in a gradient increasing mode, adjusting the pressure of the working chamber to 1-10 pa, and depositing for 3-20 min to stably deposit to form the unitary metal nitride coating;
s203, starting a second metal target, adjusting the current of the second metal target to be 50-200A, adjusting the nitrogen flow to be 100-500 sccm, applying 100-300V bias voltage to the substrate, adjusting the air pressure of the working chamber to be 1-5 pa, and depositing for 3-20 min, thereby stably depositing to form the binary metal nitride coating.
6. The method according to claim 5, wherein the first metal target is an aluminum target and the second metal target is a titanium target.
7. The method according to claim 5, wherein the increasing to 400sccm to 500sccm in a gradient increasing manner comprises flowing nitrogen gas to 180sccm to 200sccm to react nitrogen atoms with ionized target ions of the first metal target to form a nitride film, and react the nitrogen atoms with surface metal atoms of the first metal target to form a metal nitride on the surface of the first metal target; the flow rate of the nitrogen is increased to 310 sccm-330 sccm, and the nitride film forms a nano composite structure with an amorphous phase wrapped by a crystal; the flow rate of the nitrogen gas is increased to 500sccm, so that the nitrogen content in the nitride thin film is increased, and 5 crystal grains in the metal nitride coating form fine nanocrystalline particles.
8. The method for preparing a Ta-C coating layer with high compactness according to claim 1, characterized in that in step S30, the ultrasonic vibrators are uniformly distributed on the outer side of the substrate, and the number of the ultrasonic vibrators is at least 6.
9. The method for preparing a Ta-C coating layer with high compactness according to claim 1, wherein 0, the substrate is made of alloy material, and the metal nitride transition layer and the substrate have the same metal elements.
10. The method for preparing a high-density Ta-C coating according to claim 1, wherein in step S30, the carbon source gas is acetylene gas, and the inert gas is argon gas.
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| US5932302A (en) * | 1993-07-20 | 1999-08-03 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating with ultrasonic vibration a carbon coating |
| CN101113516A (en) * | 2007-08-31 | 2008-01-30 | 武汉大学 | Method for preparing nano composite diamond coating |
| CN108385066A (en) * | 2018-02-26 | 2018-08-10 | 温州职业技术学院 | A kind of hydrogen-free metal doped diamond coating production and its product |
| CN112063975A (en) * | 2020-07-28 | 2020-12-11 | 温州职业技术学院 | Method for preparing ta-C coating by modulating high-current pulse arc |
| CN115125484A (en) * | 2022-06-21 | 2022-09-30 | 东莞市华升真空镀膜科技有限公司 | Hard coating, preparation method of hard coating and coated cutting tool |
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| US5932302A (en) * | 1993-07-20 | 1999-08-03 | Semiconductor Energy Laboratory Co., Ltd. | Method for fabricating with ultrasonic vibration a carbon coating |
| CN101113516A (en) * | 2007-08-31 | 2008-01-30 | 武汉大学 | Method for preparing nano composite diamond coating |
| CN108385066A (en) * | 2018-02-26 | 2018-08-10 | 温州职业技术学院 | A kind of hydrogen-free metal doped diamond coating production and its product |
| CN112063975A (en) * | 2020-07-28 | 2020-12-11 | 温州职业技术学院 | Method for preparing ta-C coating by modulating high-current pulse arc |
| CN115125484A (en) * | 2022-06-21 | 2022-09-30 | 东莞市华升真空镀膜科技有限公司 | Hard coating, preparation method of hard coating and coated cutting tool |
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