CN113174562A - Self-organized nanostructure oxynitride hard coating and preparation method and application thereof - Google Patents
Self-organized nanostructure oxynitride hard coating and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- Organic Chemistry (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention belongs to the technical field of coating materials, and discloses a self-organized nanostructure oxynitride hard coating, and a preparation method and application thereof. The coating comprises a substrate, an AlTiN transition layer and an AlCrSiON self-organization nano multilayer from bottom to top; the AlCrSiON self-organizing nano multilayer coating is formed by alternately self-organizing a nitrogen-rich layer and an oxygen-rich layer, wherein the nitrogen-rich layer is in a nano composite structure of amorphous wrapped nano crystals. The self-organized nanostructure oxynitride coating can combine the advantages of high hardness and high toughness of the nitride coating and high thermochemical stability and high wear resistance of the oxide coating; the preparation method and the technology adopted by the invention have the advantages of convenient operation, simple process, controllable process, high deposition speed and low cost, and are suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to a self-organized nanostructure oxynitride hard coating as well as a preparation method and application thereof.
Background
The surface of the workpiece is plated with a hard coating, so that friction can be reduced, abrasion of the workpiece can be reduced, and the surface hardness, toughness, high-temperature stability and wear resistance of the product can be effectively improved, so that the service life of the product is prolonged. Modern manufacturing industry has increasingly high requirements on the performance of cutting tools, and parts used in friction environments, such as piston rings in internal combustion engines, various dies, etc., have extremely high friction losses, and the hard coating on the surface of the parts can prolong the service life of the parts. Hard coating materials have been widely used in the fields of automobile manufacturing, geological drilling, tool and die industry, marine turbines, aerospace, and the like.
Based on AlTiN and AlCrN hard coatings with good performance, researchers adopt PVD technology to prepare oxynitride hard coatings such as AlCrON and AlTiON. Based on the characteristics of good high-temperature performance stability and low thermal conductivity of the oxide coating, the high-temperature friction performance of the oxynitride coating is superior to that of the nitride coating, the thermal conductivity is reduced by 4-8 times, and the oxynitride coating has superior performance to that of the nitride coating when being applied to a cutter to cut processed materials such as stainless steel, cast iron and the like. Nevertheless, the comprehensive performance of the oxynitride coating still needs to be improved, and the nitrogen-rich oxynitride coating has a structure and performance similar to those of the nitride coating, and has poor high-temperature stability and friction performance compared with the oxide coating; and the toughness and hardness of the coating are sharply reduced when oxygen is enriched. The nitride coating and the oxide coating can be combined through the optimized structural design, so that the oxynitride hard coating has the advantages of high hardness, good toughness and excellent high-temperature performance.
Nanocomposites and nanolayers are important structural forms of nanostructured coatings. The nano composite coating is a composite structure coating formed by wrapping nano crystals in a mesh framework structure amorphous phase. Formation of the nanocomposite requires that the nanocrystalline phase and amorphous phase are immiscible with each other, for example, the AlTiSiN coating studied by Sui Xu et al is a composite structure system with both nanocrystalline phase and amorphous phase, and the nanoscale AlTiN crystal phase is wrapped in the network Si3N4In the amorphous phase, the network framework structure limits the growth of AlTiN grains, is influenced by Hall-Petch effect, achieves the effect of fine grain strengthening, and improves the mechanical properties of the coating such as hardness and the like.
The nano-multilayer coating has properties that are difficult to achieve with a single layer coating. The nano multilayer coating is formed by alternately depositing single-layer films of two or more components, and a multilayer film which completes one period every time the single-layer films are alternately deposited is called a modulation period. Due to the effects of lattice mismatch, template effect, modulus difference effect and the like between modulation layers, the nano multilayer coatingThe super-hard effect can be obtained, the hardness and the wear resistance of the coating can be obviously improved, and the toughness and the thermal stability of the coating can be improved. In many previous studies on oxynitride coatings, oxides are often present in an amorphous state, the modulus difference is not significant, the enhancement condition of the modulus difference effect is not satisfied, and the hardness of the coating is reduced due to the increase of the amorphous oxides. However, Liu Yan, Wei Li et al are studying TiN/SiO2AlTiN/AlON nano multilayer coatings have found that increased hardness can be obtained when the oxide layer is sufficiently thin to pseudomorphically grow in the nano multilayer with a nitride template. The inventor of K.Yalamarchli, P.C.Wo and the like finds that the ZrN/ZrAlN and TiN/TiSiN nano multilayer coating with high hardness and good toughness can be obtained by the synergistic effects of nano multilayer coherent strengthening, multilayer toughening, phase change toughening and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a self-organized nanostructure oxynitride hard coating; the coating comprises an AlTiN transition layer, a nitrogen-rich layer and an AlCrSiON nano multilayer coating which is formed by alternately depositing oxygen-rich layers, wherein the nitrogen-rich layer is a typical nano composite structure, so that the coating has high hardness and high toughness.
The invention also aims to provide a preparation method of the self-organized nano-structure oxynitride hard coating; the method utilizes an arc ion plating technology to prepare the AlCrSiON nano-structure coating, enables the coating to have a nano-composite and nano-multilayer structure through coating component and structure design, can regulate and control the component, the modulation structure, the phase structure and the mechanical property, and integrates various strengthening mechanisms to design and prepare the coating structure, thereby obtaining the high-hardness and high-toughness nano-structure oxynitride hard coating.
The invention further aims to provide application of the self-organized nanostructure oxynitride hard coating, which can be applied to the fields of tool and die industry, automobile manufacturing, geological drilling, ship turbines, aerospace, precise instruments and meters and the like, and has important significance for improving the manufacturing level of equipment in China.
The purpose of the invention is realized by the following technical scheme:
a self-organized nanostructured oxynitride hard coating, comprising, from bottom to top, a substrate, an AlTiN transition layer and an AlCrSiON self-organized nanolayer; the AlCrSiON self-organizing nano multilayer is formed by alternately depositing a nitrogen-rich AlCrSiON layer and an oxygen-rich AlCrSiON layer, wherein the nitrogen-rich AlCrSiON layer is a nano composite structure formed by wrapping a nanocrystal with an amorphous phase; wherein the total thickness of the coating is 2-6 μm, the modulation period is 1-100 nm, the thickness of the nitrogen-rich AlCrSiON layer is 0.1-80 nm, and the thickness of the oxygen-rich AlCrSiON layer is 0.1-20 nm.
The AlCrSiON self-organized nano multilayer contains 5-60 at% of O atoms, 4-60 at% of N atoms, 15-30 at% of Cr atoms, 13-30 at% of Al atoms and 1-10 at% of Si atoms.
The preparation method of the self-organized nanostructure oxynitride hard coating comprises the following operation steps:
cleaning a matrix: polishing the surface of the substrate, immersing the substrate in an acetone solution for ultrasonic cleaning for 10-20 min, then immersing the substrate in an absolute ethyl alcohol solution for ultrasonic cleaning for 10-20 min, and taking out the substrate for drying after the cleaning is finished;
secondly, vacuumizing: feeding the cleaned and dried substrate into a vacuum chamber, clamping the substrate on a rotating bracket, closing a chamber door, opening the rotating bracket to rotate at a rotating speed of 2-9 r/min, and pumping the vacuum degree to 4.0 multiplied by 10-3～6.0×10-3Pa, and simultaneously heating the vacuum chamber to 380-420 ℃;
thirdly, plasma etching and cleaning: when the vacuum degree of the chamber is 4.0 multiplied by 10-3～6.0×10-3After Pa, introducing Ar gas with the gas flow rate of 200-300 sccm, applying a bias voltage of-900V-1000V to the substrate, and simultaneously adjusting the gas flow rate to keep the air pressure of the chamber at 1.8-2.3 Pa, keeping the furnace temperature at 380-420 ℃ and keeping the time for 20-40 min, wherein the bias voltage duty ratio is set to 70-90%;
ion bombardment: positioning a substrate supporting rotating frame to rotate before a Cr target, setting the rotating speed to be 2-9 r/min, starting an electric arc Cr target power supply, controlling the current to be 90-110A, introducing 60-80 sccm Ar gas, adjusting the gas flow, keeping the air pressure of a chamber to be 0.6-0.8 Pa, keeping the furnace temperature to be 380-420 ℃, applying a bias voltage of-500-900V to the substrate, and bombarding ions for 3-7 min;
deposition of AlTiN transition layer: keeping the power supply of the electric arc AlTi target on, leading in N of 250-350 sccm with the current of 90-110A2Qi regulating N2The air flow keeps the air pressure of the chamber at 1.0-1.4 Pa, the furnace temperature is maintained at 380-420 ℃, the substrate bias voltage is applied at-100 to-140V, and the process is maintained for 5-10 min;
sixthly, depositing AlCrSiON self-organizing nano multilayer: turning off an AlTi target power supply, positioning the substrate supporting rotating frame to rotate before the AlCrSi target, setting the rotating speed to be 2-9 r/min, turning on an electric arc AlCrSi target power supply, setting the current to be 70-90A, and introducing N of 250-350 sccm2Introducing 0-50 sccm of O2In the process, the air pressure of a chamber is kept to be 2.8-3.2 Pa, the furnace temperature is kept to be 380-420 ℃, the deposition time is 1-3 h, a bias voltage of-130-170V is applied to the substrate, and the process self-organizes to form an AlCrSiON self-organizing nano multilayer coating in which an AlCrSiON layer rich in N and an AlCrSiON layer rich in O alternately grow;
and seventhly, after the deposition is finished, sequentially closing the electric arc target power supply, the bias power supply, the air valve and the heater power supply, and taking out the substrate after the temperature in the chamber is reduced to room temperature to obtain the self-organized nano-structure oxynitride hard coating.
The oxynitride hard coating with the self-organized nano structure is applied to the fields of tool and die industry, automobile manufacturing, geological drilling, ship and turbine, aerospace and precision instruments and meters.
The principle of the invention is as follows: the main effect of the invention is achieved by the rotation of the substrate in front of the arc target, the substrate rotates to the position near the AlCrSi target source, the plasma density is higher, and the plasma density is higher at high N2Under partial pressure, the density of N ions is far greater than that of O ions, and a thicker nitrogen-rich AlCrSiON layer is generated; the substrate rotates to a position far away from the AlCrSi target source, the plasma density is low, and the O ions have stronger reactivity and are easier to form bonds with metal ions to generate a thinner oxygen-enriched AlCrSiON layer, and the substrate rotatesUnder the autorotation action of the frame, the AlCrSiON nano multilayer coating which is formed by self-organizing nitrogen-rich layers and oxygen-rich layers alternately grows. The surface defects of the substrate are increased by using Cr ion bombardment, a Cr injection layer is obtained, the film-substrate combination is improved, the AlTiN transition layer can enable the thermal expansion coefficient of the material and the like to slowly transition from the substrate to the coating, and therefore the film-substrate internal stress and the film-substrate combination force are improved. The AlCrSiON self-organizing nano-structure functional layer can integrate the characteristics of various strengthening mechanisms such as poor modulus strengthening, nano composite strengthening, nano multi-layer strengthening, coherent strengthening and the like, improve the toughness and hardness of the coating, and simultaneously effectively reduce the internal stress of the coating.
Compared with the prior art, the invention has the following advantages and effects:
(1) the self-organized oxynitride nanostructure coating can combine the advantages of high hardness and high toughness of a nitride coating and high thermochemical stability and high wear resistance of an oxide coating;
(2) the invention forms AlCrSiON nano multilayer which is formed by self-organizing and alternately growing the nitrogen-rich layer and the oxygen-rich layer through the rotation control of the substrate bracket, and the adopted preparation method and the technology have the advantages of convenient operation, simple process, controllable process, high deposition speed and low cost, and are suitable for large-scale industrial production.
(3) The invention adopts the arc ion plating technology to design a novel self-organizing multi-component multilayer oxynitride hard coating which integrates self-organizing oxynitride nano multilayer, a nano composite structure and self-adapting surface structure.
Drawings
Fig. 1 is a schematic structural diagram of the coatings obtained in examples 1 to 5 and comparative document 1, wherein (a) is a schematic structural diagram of an AlCrSiON self-organized nano-structured coating provided in examples 1 to 5 of the present invention, the coating is composed of AlCrSiON self-organized nano-multilayer functional layers alternately deposited by an AlTiN transition layer, a nitrogen-rich layer and an oxygen-rich layer, wherein the nitrogen-rich layer is a nano-composite structure formed by typical nanocrystals being wrapped by an amorphous phase; (b) the AlCrSiN coating structure is provided for a comparative example.
FIG. 2 shows X-ray diffraction patterns of AlCrSiON nanostructure coatings provided in examples 1 to 5 of the present invention and AlCrSiN coatings provided in comparative examples; from the figureIt can be seen that hexagonal AlN phase diffraction peaks were not detected in all the coatings provided in examples 1 to 5 and comparative examples of the present invention, and the coatings were all face-centered cubic structures. No SiO was detected in the XRD pattern of all coatings2Or Si3N4Diffraction peaks, indicating the presence of Si in the coating in the form of an amorphous phase.
FIG. 3 is a SEM cross-sectional view of the coating obtained in comparative example and examples 1-5, wherein (a) is the SEM cross-sectional view of the AlCrSiN coating obtained in comparative example, and (b), (c), (d), (e), and (f) are the SEM cross-sectional views of the AlCrSiON self-organized nanostructure coating obtained in examples 1-5, respectively; as can be seen from the cross-sectional SEM images, all coatings bond well to the substrate, the AlCrSiN coatings and the AlCrSiON coatings described in examples 1, 2 with an oxygen inlet flow rate below 11 seem exhibit a pronounced columnar grain growth morphology, and the AlCrSiON coatings described in examples 3, 4, 5 with an oxygen inlet flow rate above 11 seem exhibit a glassy growth morphology.
FIG. 4 is a TEM analysis of two representative coatings selected from the coatings according to the embodiments of the present invention, wherein FIG. 4-1 is N described in example 12/O2TEM image of AlCrSiON coating with gas flow rate of 291/9, it can be seen from fig. 4-1(a) that the coating is a nano multilayer structure; from the EDS results of the coating elements of FIG. 4-1(c), it can be seen that the N element and O element exhibit periodic variations in the multilayer structure with a modulation period of 11.6nm, with the thicker (10.7nm) layer being rich in the N element and the thinner (0.9nm) layer being rich in the O element; the circle-framed region in fig. 4-1(b) is an atomic ordered arrangement of nanocrystals that are encapsulated by an amorphous phase with an atomic disordered arrangement outside the circle frame, which indicates that the thicker N-rich layer in the AlCrSiON coating forms a typical nanocomposite structure; FIG. 4-2 shows N as described in example 42/O2TEM image of AlCrSiON coating with gas flow rate of 279/21, and it can be seen from FIGS. 4-2(a), (b) that the coating is a nano-multilayer structure; from the EDS results of the coating elements of FIGS. 4-2(c), it can be seen that the N element and the O element exhibit periodic variations in the multilayer structure, with a modulation period of 11.6nm, a thicker (9.2nm) layer rich in the N element, and a thinner (2.4nm) layer rich in the O element; it can be seen from FIGS. 4-1(a) and 4-2(a) that the local region at the boundary of the N-rich layer and the O-rich layer isExhibit the characteristics of coherent epitaxial growth.
FIG. 5 shows the results of mechanical property tests of AlCrSiN coatings obtained in comparative examples and AlCrSiON nanostructure coatings obtained in examples 1 to 5; with O in the course of the coating preparation2The flow rate was increased and the hardness of the coating was increased and then decreased, N being described in example 12/O2The AlCrSiON coating with a gas flow ratio of 291/9 reached a maximum value of 36GPa, compared to the AlCrSiN (i.e.N) of the comparative example2/O 2300/0) coating hardness of 31GPa is obviously improved, and N is described in example 42/O2The AlCrSiON coating with a gas flow ratio of 279/21 also has a higher hardness (-30 GPa); the reason why the small amount of oxygen-doped hardness is improved may be related to the coating structure design related to the present invention, and it can be known from the TEM results that the coatings of examples 1 to 5 form a nano multilayer structure in which nitrogen-rich layers and oxygen-rich layers alternate due to the rotational self-organization of the substrate, and the multilayer interface hinders the movement of dislocations; the TEM examination results show that N is described in example 12/O2The N-rich layer in the AlCrSiON coating with the gas flow ratio of 291/9 forms an obvious nano composite structure, namely the coating combines nano multilayer strengthening and nano composite strengthening effects, so that the hardness of the coating is improved; h3/E*2The values are often used to characterize the toughness of the coatings, and it can be seen from FIG. 5 that H of the AlCrSiON coatings described in examples 1 to 5 of the invention3/E*2Both values are greater than the AlCrSiN coatings described in the comparative examples, while the self-organized nano-multilayer structure and the localized co-extensive epitaxial growth are the main reasons for the better toughness of the AlCrSiON nanostructured coatings compared to the AlCrSiN coatings.
Detailed Description
The following further describes the present invention with reference to specific examples and drawings, but the present invention should not be construed as being limited thereto. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A self-organized nano-structure oxynitride hard coating comprises an AlTiN transition layer and AlCrSiON self-organized nano-multilayer (nitrogen-enriched AlCrSiON layer and oxygen-enriched AlCrSiON layer which are alternately grown), wherein the nitrogen gas inlet flow rate is 291sccm, the oxygen gas inlet flow rate is 9sccm when the AlCrSiON self-organized nano-multilayer is deposited, the nitrogen atom content of the finally obtained coating is 40.7 at.%, the oxygen atom content is 9.8 at.%, the aluminum atom content is 20.5 at.%, the chromium atom content is 26.0 at.%, the silicon atom content is 3.0 at.%, the thickness of the coating is 2.8 mu m, the thickness of the nitrogen-enriched AlCrSiON layer (also called nitrogen-enriched layer) is 10.7nm, the thickness of the oxygen-enriched AlCrSiON layer (also called oxygen-enriched layer) is 0.9nm, and the modulation period is 11.6 nm. The preparation method comprises the following steps:
polishing the surface of the substrate, immersing the substrate in an acetone solution for ultrasonic cleaning for 15min, then immersing the substrate in an absolute ethyl alcohol solution for ultrasonic cleaning for 15min, taking out the substrate after cleaning, and drying the substrate; feeding the cleaned and dried substrate into a vacuum chamber, clamping the substrate on a rotary bracket, closing a chamber door, opening the rotary bracket for autorotation at a rotation speed of 3r/min, and pumping the vacuum degree to 5.0 × 10-3While heating the vacuum chamber to 400 ℃; when the vacuum degree of the chamber is 5.0 multiplied by 10-3Then, introducing Ar gas with the gas flow of 300sccm, applying a bias voltage of-1000V to the substrate, and simultaneously adjusting the gas flow to keep the vacuum degree of the chamber at 2.1Pa, the furnace temperature at 400 ℃ and the duration for 30min, wherein the bias voltage duty ratio is set to 80%; positioning a substrate supporting rotating frame to rotate before a Cr target, setting the rotating speed at 3r/min, starting an arc Cr target power supply, introducing Ar gas of 70sccm, adjusting the gas flow, maintaining the vacuum degree of a chamber at 0.7Pa, keeping the furnace temperature at 400 ℃, applying a bias voltage of-800V to the substrate, after bombarding for 2min, adjusting the bias voltage of the substrate to-600V, and bombarding for 3 min; the power supply of the arc Cr target is turned off, and the arc Al is turned on50Ti50The target power supply with the current of 100A is introduced into N of 300sccm2Qi regulating N2The air flow is controlled to keep the vacuum degree of the chamber at 1.2Pa, the furnace temperature is maintained at 400 ℃, the substrate bias voltage is applied to 120V, and the process is maintained for 10 min; deposition of AlCrSiON self-organized nano-multilayers: shutting off Al50Ti50Target power source to position the substrate support turret to Al45Cr45Si10Autorotation before the target, setting the rotating speed at 3r/min, and starting an electric arc Al45Cr45Si10A target power supply with a current of 80A and N of 291sccm2Gas, introducing O of 9sccm2Applying a bias voltage of-150V to the substrate, keeping the vacuum degree of a chamber at 3.0Pa, maintaining the furnace temperature at 400 ℃, and depositing for 1h, wherein the AlCrSiON nano multilayer coating with alternately grown N-rich layers and O-rich layers is formed in the process in a self-organizing manner; and after the deposition is finished, sequentially closing the electric arc target power supply, the bias power supply, the air valve and the heater power supply, and taking out the substrate after the temperature in the chamber is reduced to room temperature to obtain the self-organized nano-structure oxynitride hard coating.
Examples 2 to 5
The preparation method of the coating described in the embodiments 2 to 5 is basically the same as that of the embodiment 1, except that the flow rate of nitrogen and the flow rate of oxygen introduced in the preparation process of the coating are different, and the specific operation parameters are shown in table 1.
The coatings obtained in examples 2-5 are substantially the same as those obtained in example 1, except that the contents of nitrogen atoms and oxygen atoms in the obtained coatings are different, and specific parameters are shown in Table 1.
Comparative example
Comparative example the preparation method of the coating described in the comparative example is substantially the same as in examples 1 to 5, except that no oxygen was introduced during the preparation of the coating, the nitrogen flow was 300sccm, and the oxygen flow was 0 sccm.
The coatings obtained in the comparative example are basically the same as the coatings obtained in the examples 1-5, and the difference is that the contents of nitrogen atoms and oxygen atoms in the obtained coatings are different, and specific parameters are shown in Table 1.
TABLE 1 Nitrogen atom and oxygen atom contents in the coatings of comparative example and examples 1 to 5
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A self-organizing nanostructured oxynitride hard coating characterized by: the coating comprises a substrate, an AlTiN transition layer and an AlCrSiON self-organization nano multilayer from bottom to top; the AlCrSiON self-organizing nano multilayer is formed by alternately depositing a nitrogen-rich AlCrSiON layer and an oxygen-rich AlCrSiON layer, wherein the nitrogen-rich AlCrSiON layer is a nano composite structure formed by wrapping a nanocrystal with an amorphous phase; wherein the total thickness of the coating is 2-6 μm, the modulation period is 1-100 nm, the thickness of the nitrogen-rich AlCrSiON layer is 0.1-80 nm, and the thickness of the oxygen-rich AlCrSiON layer is 0.1-20 nm.
2. A self-organizing nanostructured oxynitride hard coating according to claim 1 characterized in that: the AlCrSiON self-organized nano multilayer contains 5-60 at% of O atoms, 4-60 at% of N atoms, 15-30 at% of Cr atoms, 13-30 at% of Al atoms and 1-10 at% of Si atoms.
3. The method for preparing a self-organized nano-structured oxynitride hard coating according to claim 1, characterized by the following steps:
cleaning a matrix: polishing the surface of the substrate, immersing the substrate in an acetone solution for ultrasonic cleaning for 10-20 min, then immersing the substrate in an absolute ethyl alcohol solution for ultrasonic cleaning for 10-20 min, and taking out the substrate for drying after the cleaning is finished;
secondly, vacuumizing: feeding the cleaned and dried substrate into a vacuum chamber, clamping the substrate on a rotating bracket, closing a chamber door, opening the rotating bracket to rotate at a rotating speed of 2-9 r/min, and pumping the vacuum degree to 4.0 multiplied by 10-3～6.0×10-3Pa, and simultaneously heating the vacuum chamber to 380-420 ℃;
thirdly, plasma etching and cleaning: when the vacuum degree of the chamber is 4.0 multiplied by 10-3～6.0×10-3After Pa, a gas stream is introducedAr gas with the amount of 200-300 sccm is used for applying a bias voltage of-900V-1000V to the substrate, and meanwhile, the gas flow is adjusted, so that the air pressure of a chamber is kept at 1.8-2.3 Pa, the furnace temperature is kept at 380-420 ℃, the duration time is 20-40 min, and the bias voltage duty ratio is set to be 70-90%;
ion bombardment: positioning a substrate supporting rotating frame to rotate before a Cr target, setting the rotating speed to be 2-9 r/min, starting an electric arc Cr target power supply, controlling the current to be 90-110A, introducing 60-80 sccm Ar gas, adjusting the gas flow, keeping the air pressure of a chamber to be 0.6-0.8 Pa, keeping the furnace temperature to be 380-420 ℃, applying a bias voltage of-500-900V to the substrate, and bombarding ions for 3-7 min;
deposition of AlTiN transition layer: keeping the power supply of the electric arc AlTi target on, leading in N of 250-350 sccm with the current of 90-110A2Qi regulating N2The air flow keeps the air pressure of the chamber at 1.0-1.4 Pa, the furnace temperature is maintained at 380-420 ℃, the substrate bias voltage is applied at-100 to-140V, and the process is maintained for 5-10 min;
sixthly, depositing AlCrSiON self-organizing nano multilayer: turning off an AlTi target power supply, positioning the substrate supporting rotating frame to rotate before the AlCrSi target, setting the rotating speed to be 2-9 r/min, turning on an electric arc AlCrSi target power supply, setting the current to be 70-90A, and introducing N of 250-350 sccm2Introducing 0-50 sccm of O2In the process, the air pressure of a chamber is kept to be 2.8-3.2 Pa, the furnace temperature is kept to be 380-420 ℃, the deposition time is 1-3 h, a bias voltage of-130-170V is applied to the substrate, and the process self-organizes to form an AlCrSiON self-organizing nano multilayer coating in which an AlCrSiON layer rich in N and an AlCrSiON layer rich in O alternately grow;
and seventhly, after the deposition is finished, sequentially closing the electric arc target power supply, the bias power supply, the air valve and the heater power supply, and taking out the substrate after the temperature in the chamber is reduced to room temperature to obtain the self-organized nano-structure oxynitride hard coating.
4. Use of a self-organizing nanostructured oxynitride hard coating according to claim 1 in the fields of tool and die industry, automotive manufacturing, geological drilling, marine turbines, aerospace, precision instrumentation.
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