CN115821205A - High-entropy alloy nitride nano composite structure hard coating with adjustable structural components and preparation method thereof - Google Patents
High-entropy alloy nitride nano composite structure hard coating with adjustable structural components and preparation method thereof Download PDFInfo
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- CN115821205A CN115821205A CN202211528381.1A CN202211528381A CN115821205A CN 115821205 A CN115821205 A CN 115821205A CN 202211528381 A CN202211528381 A CN 202211528381A CN 115821205 A CN115821205 A CN 115821205A
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Abstract
The invention relates to a high-entropy alloy nitride nano composite structure hard coating with adjustable structural components and a preparation method thereof, wherein the preparation method of the coating comprises the following steps: 1) Bombarding and activating the etching substrate by using high-intensity plasma; 2) Sputtering a transition layer on an etching substrate by taking Cr as a target material; 3) And sputtering and depositing a hardened layer on the transition layer by using TiVCrNbSiTaBY high-entropy alloy as a target. In order to regulate and control the components and the structure of the deposited coating, the invention reasonably designs the sputtering target material to fully utilize the higher sputtering yield of the light-weight atoms in the magnetron sputtering processOne characteristic is that sputtering energy borne by the sputtering target is adjusted by changing parameters such as magnetron sputtering power and the like, so that the proportion of light-weight atoms, namely Si atoms, in the high-entropy alloy target is regulated and controlled, and amorphous Si formed by the Si atoms and N atoms is further changed 3 N 4 The content of the structure, thereby regulating and controlling the component structure of the deposited coating.
Description
Technical Field
The invention relates to the technical field of hard coating preparation, in particular to a high-entropy alloy nitride nano composite structure hard coating with adjustable structural components and a preparation method thereof.
Background
Cutting tools are known as "industrial teeth" and have irreplaceable important roles in modern industrial manufacturing. Hard alloy and high-speed steel are the most commonly used cutting tools, however, the working efficiency and service life of mechanical parts and equipment are seriously affected by the problems of high temperature, friction and the like generated in the machining process, and the parts can rapidly lose efficacy due to serious abrasion damage, so that huge resource consumption and economic loss are caused. Therefore, the demands on the mechanical properties and the service life of the cutting tools are also increasing.
The surface hard coating treatment is an effective means for improving the processing efficiency and prolonging the service life of the cutter. The hard coating is prepared by Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD). The coating prepared by the CVD technology has high purity and good adhesion with a substrate, and is suitable for parts with complex shapes and coating films for depositing inner walls, inner holes and the like. However, CVD techniques generally require very high reaction temperatures (900-1000 ℃ C.), limiting their further applications. Compared with CVD technology, the PVD method has lower deposition temperature, is particularly suitable for the preparation of coatings of precise and complex tools, and is widely applied to the preparation of tool coatings.
Transition metal nitrides generally have high hardness, excellent wear resistance, good thermal stability and corrosion resistance, and are therefore widely used in protective coatings for tools. TiN was the first PVD coating developed and has been widely used for tool protective coatings in the past decades due to its good combination of properties. With the rapid development of manufacturing industry, the traditional binary nitride coating can not meet the requirement, and alloying is an important direction for the development of hard tool coatings. The hardness, toughness, wear resistance, oxidation resistance and the like of the coating can be effectively enhanced by adding alloy elements to form multi-nitride.
High Entropy Alloys (HEA) are alloy systems composed of at least five elements in equal or nearly equal atomic ratios, each element being present in concentrations between 5% and 35%. High Entropy Alloy Nitrides (HEAN) tend to form simple solid solution structures of Face Centered Cubic (FCC) or Body Centered Cubic (BCC) based on high entropy effects. The severe lattice distortion caused by the large atomic size difference reduces the cooperative diffusion of different elements, and further promotes the formation of nanocrystalline and even amorphous structures. The high-entropy nitride alloy coating has the new characteristics of slow diffusion rate, good thermal stability, excellent high-temperature mechanical strength and the like, so that the high-entropy nitride alloy coating quickly becomes a new research hotspot for industrial application in the last decade.
The composition and the structure of the high-entropy alloy coating material have great influence on the performance of the high-entropy alloy coating material, and the preparation processes under different parameters generate complex change rules on the composition and the structure of the coating. In order to meet specific performance requirements, high-entropy alloy targets with different components even need to be designed, and the cost in the coating preparation process is greatly increased. Therefore, how to regulate and control the component structure of the hard coating by a simple and effective method so as to improve the performance of the hard coating becomes the focus of the current research.
Disclosure of Invention
Aiming at the problems, the high-entropy alloy nitride nano composite structure hard coating with adjustable structural components and the preparation method thereof are provided, the component structure of the coating can be controlled and adjusted, and the requirements of industrial cutting tools under different use requirements can be met.
In order to regulate and control the components and the structure of a deposited coating, the sputtering target is reasonably designed by the invention, so that the characteristic that the sputtering yield of light-weight atoms is higher in the magnetron sputtering process is fully utilized, the sputtering energy borne by the sputtering target is regulated by changing parameters such as magnetron sputtering power and the like, the proportion of light-weight atoms, namely Si atoms, in the high-entropy alloy target is changed, and further, amorphous Si formed by the Si atoms and N atoms is changed 3 N 4 The amount of structure, and thus the composition and structure of the deposited coating.
The beneficial effect of above-mentioned scheme is:
1) The high-entropy alloy target provided by the invention can synthesize (TiVCrNbSiTaBY) N coating material in a nitrogen environment, so that not only is waste caused by using a plurality of targets avoided in the prior art, but also the components and the structure of a deposited coating can be adjusted by utilizing the nitrogen content as required;
2) The invention fully utilizes the characteristic of high yield of light-weight atomic sputtering, and achieves the purpose of regulating and controlling the components and the structure of the coating by changing the effect of sputtering energy amplification on the sputtering target;
3) According to the invention, appropriate preparation parameters can be selected only according to the application and performance requirements of the target coating so as to effectively regulate and control the structure and components of the corresponding coating, thereby meeting the preparation requirements of hard coatings and other functional coatings.
Drawings
FIG. 1 is a schematic view of a radio frequency magnetron sputtering apparatus used in the preparation of a hard coating according to the present invention;
FIG. 2 is a surface topography of a hard coating prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional profile of a hard coating prepared in example 1 of the present invention;
FIG. 4 is a high resolution transmission profile and a nanocomposite structure schematic of a hard coating prepared in example 1 of the present invention;
FIG. 5 is a graph showing the change law of Si element content in a hard coating prepared by setting different magnetron sputtering powers under the condition of the embodiment 1;
FIG. 6 is a graph showing the change law of the nano-hardness and the elastic modulus of a hard coating prepared by setting different magnetron sputtering powers under the condition of the embodiment 1;
in the drawings: 1. a radio frequency power supply and a sputtering target material; 2. an arc power supply and a target material; 3. a baffle plate; 4. a sample holder; 5. a heater; 6. a vacuum system; 7. an air duct.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is further described with reference to the following drawings and specific examples, which are not intended to be limiting.
The preparation method of the hard coating with the TiVCrNbSiTaBYN high-entropy alloy nitride nano composite structure comprises the following steps:
1) Preparing and forming a TiVCrNbSiTaBY high-entropy alloy target: mixing Ti: v: cr: nb: si: ta: b: the powder of the Y eight elements is mixed and sintered according to the atomic ratio of 26;
2) Pre-cleaning the substrate: respectively ultrasonically cleaning the substrate in acetone, ethanol and deionized water for 10 minutes to remove dust, organic matters and other stubborn pollutants on the surface of the substrate, then drying the substrate in a nitrogen atmosphere, and quickly filling the substrate into a vacuum chamber to prevent secondary pollution;
3) Preparing an experimental environment: in turn in a radio frequency magnetron sputtering devicePlacing a radio frequency power supply and sputtering target 1, an arc power supply and target 2, a sample holder 4 and a substrate (namely a sample), wherein the substrate is parallel to the arc power supply target 2, and the sputtering target 1 is vertical to the arc power supply target 2; the cooling system is started, vacuum is pumped through the vacuum system 6, and the heater 5 is simultaneously turned on, so that the vacuum degree in the chamber is enabled to be generally 10 -3 Pa magnitude), temperature (the temperature is determined by the coating application and performance and generally ranges from 100 ℃ to 300 ℃) to reach ideal values;
4) Substrate etching: introducing high-purity Ar gas through the ventilation pipeline 7, setting the negative bias and the duty ratio of the substrate, starting the arc power supply 2, forming electric arc enhanced glow discharge under the action of the voltage difference, and ionizing Ar into Ar + ，Ar + The ion beam bombards the substrate at a potential difference to remove oxides from the surface of the substrate and activate the surface to increase the bonding force between the substrate and the coating (in order to protect the substrate from the Cr sputtered from the arc power source target 2) + Influence, the arc power source target 2 is provided with the baffle 3 in the etching process, and the baffle 3 is in a closed state, thereby realizing Cr + Blocking);
5) Depositing a transition layer: after the etching of the substrate is finished, the baffle 3 is opened, and Cr is sputtered in the arc power source target 2 at the moment + Depositing the hard coating on a substrate to form a uniform Cr layer so as to improve the bonding force of the hard coating to be deposited;
6) And (3) hard coating deposition: turning off the arc power supply 2, rotating the sample holder 4 clockwise by 90 degrees to enable the substrate to be parallel to the sputtering target 1, and controlling the distance between the substrate and the sputtering target 1 according to requirements (specifically adjusting according to set experimental parameters); turning on the radio frequency power supply 1 and setting parameters, introducing high-purity Ar gas and high-purity nitrogen gas with the concentration of 99.99 percent into the chamber through the ventilation pipeline 7, wherein the Ar/N is 2 Under the action of the mixed gas flow and the radio frequency source, substances in the sputtering target material 1 are sputtered and deposited on the substrate to form a hard coating which is uniformly coated on the surface of the substrate;
7) Cooling system and sample: and stopping film deposition after the experiment reaches the set deposition time, sequentially closing the radio frequency power supply 1, the vent pipeline 7, the heater 5 and the vacuum system 6, cooling to room temperature, closing the cooling system, taking out the sample, and finishing the preparation of the hard coating.
Example 1
After the substrate is cleaned preliminarily and the magnetron sputtering equipment is placed, the vacuum degree in the cavity is adjusted to 3 multiplied by 10 -3 Pa, regulating the temperature to 250 ℃; introducing high-purity Ar gas until the air pressure in the chamber is 1.0Pa, starting the sample holder to rotate, setting the negative bias voltage of-200V and the duty ratio of 80 percent of the substrate, starting an arc power supply and current of 80A, and carrying out plasma etching on the substrate to deeply clean the substrate; opening the Cr target baffle after the etching is finished, and depositing a Cr transition layer with the thickness of about 100 nm; turning off the arc power supply and the Cr target baffle, rotating the sample holder to make the substrate parallel to the sputtering target, and introducing Ar: N 2 1, controlling the air pressure in the chamber to be 0.8Pa, turning on a radio frequency power supply, adjusting the radio frequency power to be 800W, and controlling the power to be in Ar/N ratio in the Ar/N ratio range 2 Sputtering a sputtering target material and depositing the sputtering target material to the substrate under the action of the mixed gas flow and the radio frequency source, and controlling the deposition time to form a hard coating which is about 1um and uniformly wraps the surface of the substrate; and closing the magnetron sputtering equipment after the preparation is finished, and naturally cooling to room temperature to obtain the high-entropy alloy nitride nano composite structure hard coating.
Example 2
After the substrate is cleaned preliminarily and the magnetron sputtering equipment is placed, the vacuum degree in the cavity is adjusted to 3 multiplied by 10 -3 Pa, regulating the temperature to 200 ℃; introducing high-purity Ar gas until the pressure in the chamber is 2.0Pa, starting the sample holder to rotate, setting the negative bias voltage of-150V and the duty ratio of 80 percent of the substrate, starting an arc power supply and the current of 80A, and carrying out plasma etching on the substrate to deeply clean the substrate; opening the Cr target baffle after the etching is finished, and depositing a Cr transition layer with the thickness of about 100 nm; turning off the arc power supply and the Cr target baffle, rotating the sample holder to make the substrate parallel to the sputtering target, and introducing Ar: N 2 The mixed gas flow is 2, the air pressure in the chamber is controlled to be 1.0Pa, the radio frequency power supply is turned on, the radio frequency power is regulated to be 700W, and the mixed gas flow is controlled to be in Ar/N ratio 2 Sputtering a sputtering target material and depositing the sputtering target material to the substrate under the action of the mixed gas flow and the radio frequency source, and controlling the deposition time to form a hard coating which is about 1um and uniformly wraps the surface of the substrate; and closing the magnetron sputtering equipment after the preparation is finished, and naturally cooling to room temperature to obtain the high-entropy alloy nitride nano composite structure hard coating.
Example 3
After the substrate is cleaned preliminarily and the magnetron sputtering equipment is placed, the vacuum degree in the cavity is adjusted to 3 multiplied by 10 -3 Pa, regulating the temperature to 300 ℃; introducing high-purity Ar gas until the pressure in the chamber is 2.0Pa, starting the sample holder to rotate, setting the negative bias voltage of-100V and the duty ratio of 80 percent of the substrate, starting an arc power supply and current of 80A, and carrying out plasma etching on the substrate to deeply clean the substrate; opening the Cr target baffle after the etching is finished, and depositing a Cr transition layer with the thickness of about 100 nm; turning off the arc power supply and the Cr target baffle, rotating the sample holder to make the substrate parallel to the sputtering target, and introducing Ar: N 2 The mixed gas flow is 1 2 Sputtering a sputtering target material and depositing the sputtering target material to the substrate under the action of the mixed gas flow and the radio frequency source, and controlling the deposition time to form a hard coating which is about 1um and uniformly wraps the surface of the substrate; and closing the magnetron sputtering equipment after the preparation is finished, and naturally cooling to room temperature to obtain the high-entropy alloy nitride nano composite structure hard coating.
Example 4
After the substrate is cleaned preliminarily and the magnetron sputtering equipment is placed, the vacuum degree in the cavity is adjusted to 3 multiplied by 10 -3 Pa, regulating the temperature to 150 ℃; introducing high-purity Ar gas until the air pressure in the chamber is 2.0Pa, starting the sample holder to rotate, setting the negative bias voltage of-250V and the duty ratio of 80 percent of the substrate, starting an arc power supply and the current of 80A, and carrying out plasma etching on the substrate to deeply clean the substrate; opening the Cr target baffle after the etching is finished, and depositing a Cr transition layer with the thickness of about 100 nm; turning off the arc power supply and the Cr target baffle, rotating the sample holder to make the substrate parallel to the sputtering target, and introducing Ar: N 2 1, controlling the air pressure in the chamber to be 1.5Pa, turning on a radio frequency power supply, adjusting the radio frequency power to be 600W, and controlling the power to be in Ar/N ratio 2 Sputtering a sputtering target material and depositing the sputtering target material to the substrate under the action of the mixed gas flow and the radio frequency source, and controlling the deposition time to form a hard coating which is about 1um and uniformly wraps the surface of the substrate; and closing the magnetron sputtering equipment after the preparation is finished, and naturally cooling to room temperature to obtain the high-entropy alloy nitride nano composite structure hard coating.
Example 5
After the substrate is cleaned preliminarily and the magnetron sputtering equipment is placed, the vacuum degree in the cavity is adjusted to 3 multiplied by 10 -3 Pa, regulating the temperature to 100 ℃; introducing high-purity Ar gas until the air pressure in the chamber is 3.0Pa, starting the sample holder to rotate, setting the negative bias voltage of-300V and the duty ratio of 80 percent of the substrate, starting an arc power supply and the current of 80A, and carrying out plasma etching on the substrate to deeply clean the substrate; opening the Cr target baffle after the etching is finished, and depositing a Cr transition layer with the thickness of about 100 nm; the arc power supply and the Cr target baffle are closed, the sample holder is rotated to ensure that the substrate is parallel to the sputtering target, and Ar: N is introduced 2 The mixed gas flow is 2, the air pressure in the chamber is controlled to be 1.5Pa, the radio frequency power supply is turned on, the radio frequency power is adjusted to be 600W, and the mixed gas flow is controlled to be in Ar/N ratio 2 Sputtering a sputtering target material and depositing the sputtering target material to the substrate under the action of the mixed gas flow and the radio frequency source, and controlling the deposition time to form a hard coating which is about 1um and uniformly wraps the surface of the substrate; and closing the magnetron sputtering equipment after the preparation is finished, and naturally cooling to room temperature to obtain the high-entropy alloy nitride nano composite structure hard coating.
As shown in FIG. 2, the coating prepared in example 1 has a dense and smooth surface without obvious defects.
As shown in FIG. 3, the coating (including a Cr transition layer of about 100 nm) prepared in example 1 is tightly bonded to the substrate without any significant pores, which indicates that the coating has good bonding force and can meet the application requirements.
As can be seen from FIG. 4, the microstructure of the coating is obviously changed after the power of the radio frequency power supply is changed, more amorphous structures can be observed along with the increase of the radio frequency power, the grain refinement can reach 5nm, and the grain refinement is combined with the element composition (namely, amorphous Si) in the coating 3 N 4 Structure) and the Si element content variation in fig. 5, demonstrate the controllable coating structure of the present invention.
As can be seen from FIG. 5, the content of Si in the coating layer is significantly changed after the power of the RF power source is changed in the present invention, thereby proving that the present invention can regulate the coating composition.
As can be seen from FIG. 6, the nano-hardness and the elastic modulus of the coating are obviously changed after the power of the radio frequency power supply is changed, so that the performance of the coating can be improved by regulating and controlling the components and the structure of the coating.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of a high-entropy alloy nitride nano composite structure hard coating with adjustable structural components is characterized by comprising the following steps:
1) Bombarding and activating the etching substrate by using high-intensity plasma;
2) Sputtering a transition layer on an etching substrate by taking Cr as a target material;
3) And sputtering and depositing a hardened layer on the transition layer by using TiVCrNbSiTaBY high-entropy alloy as a target.
2. The method according to claim 1, wherein the power of the RF magnetron sputtering, the gas pressure in the chamber, and Ar/N are adjusted 2 The ratio of the light-weight atoms in the high-entropy alloy target material to be sputtered is changed, so that the components and the structure of the deposited coating are regulated and controlled.
3. The method of claim 2, wherein the RF magnetron sputtering power is adjusted to 500-900W, the pressure in the chamber is 0.5-2Pa, ar/N 2 Between 1:5 to 5:1.
4. the production method according to any one of claims 1 to 3, characterized in that it is produced by mixing and sintering powders of Ti, V, cr, nb, si, ta, B, Y in an atomic ratio of 26.
5. A high-entropy alloy nitride nanocomposite structure hard coating with adjustable and controllable structural components, which is prepared according to the preparation method of claims 1-4.
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| CN202211528381.1A CN115821205A (en) | 2022-11-30 | 2022-11-30 | High-entropy alloy nitride nano composite structure hard coating with adjustable structural components and preparation method thereof |
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