CN113403578A - Preparation method of superhard multilayer nano composite coating - Google Patents
Preparation method of superhard multilayer nano composite coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000000151 deposition Methods 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000005498 polishing Methods 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052786 argon Inorganic materials 0.000 claims abstract description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 15
- 230000007704 transition Effects 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 8
- 239000010432 diamond Substances 0.000 claims abstract description 8
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- 238000000992 sputter etching Methods 0.000 claims abstract description 6
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- 230000008021 deposition Effects 0.000 claims description 31
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- -1 argon ions Chemical class 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 5
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- 229910045601 alloy Inorganic materials 0.000 claims description 3
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- 238000007373 indentation Methods 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
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- 238000002474 experimental method Methods 0.000 abstract description 2
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- 238000001000 micrograph Methods 0.000 description 4
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- 238000005137 deposition process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 230000008569 process Effects 0.000 description 2
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- 238000004544 sputter deposition Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- 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
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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Abstract
The invention discloses a method for preparing an ultrahard multilayer nano composite coating, which comprises the following steps: 1) performing mirror polishing and ultrasonic cleaning on the substrate; 2) cleaning the surface of the base material by using argon ion etching; 3) depositing a transition Cr layer; 4) depositing a CrN layer; 5) and depositing a CrTiSiN layer. The method comprises the following steps of 1) performing mirror polishing and ultrasonic cleaning on a base material, specifically, performing mirror polishing on the base material on a metallographic polishing machine, firstly performing rough polishing by using w20 diamond powder and matching with rough polishing canvas, then performing fine polishing by using w2.5 diamond powder and matching with fine polishing flannelette, and performing ultrasonic cleaning in an alcohol solution for 20-30 minutes after the base material is cleaned by fine polishing. The ultra-hard hardness value can be obtained more easily in a lower Si content range; coating with Al2O3The ball is subjected to a friction experiment, and shows that the ball has a lower wear rate and reduces energy loss; and the nano indentation is carried out, so that no defect occurs, and the toughness is good.
Description
Technical Field
The invention relates to the field of coating preparation, in particular to a preparation method of an ultrahard multilayer nano composite coating.
Background
Of the losses of energy, the losses in the form of frictional wear account for about 30% thereof, while about 80% of the component failures are also due to various forms of wear. What is needed isTherefore, the core problem of improving the machining precision and the operation stability of the mechanical equipment and prolonging the service life is to reduce or reduce the abrasion of various parts in the mechanical equipment. According to Archard abrasion model calculation formula
The wear volume (V) of a material is inversely proportional to its hardness (H), so it is generally accepted that hardness is a direct indicator of the wear resistance of a material, resulting in ultrahardness (H)>40GPa) coatings are the goal of researchers. Currently, the nanocomposite concept has been applied to the design of multi-component transition metal nitride coatings by introducing amorphous silicon nitride or amorphous boron nitride phases to refine the grain size of the coating to improve its mechanical and thermal properties. Transition metal nitride based coatings (MeXN, Me: Cr, Ti; X: Si, B) are coating materials with hard characteristics, have the advantages of low residual internal stress, strong film-substrate binding force, strong oxidation resistance, strong corrosion resistance and the like, and are commonly used for surface protection of mechanical parts and cutter coatings. Compared with ternary TiSiN and CrSiN coatings, TiSiN can obtain higher hardness, but the toughness and the oxidation resistance are poorer, and in contrast, stable Cr can be formed due to the fact that Cr atoms migrate to the surface2O3The layer, CrSiN coating, has good high temperature oxidation and corrosion resistance properties, but is generally less hard than TiSiN coatings. Therefore, researches have found that the Ti-Cr-Si-N composite coating has better practical performance than the ternary composite coating.
Researchers have attempted to prepare Cr-Ti-Si-N quaternary coatings to further improve coating hardness and other properties:
[1]e.g. B.S.Lou, etc. using high power pulse magnetron sputtering technique, Ti(10％)The power of the Cr target is 300W, Ar is N2The gas flow is 30:3, the base material bias is-150V, the base material temperature is 200 ℃, the Si target power (50, 75, 100, 125, 150W) is changed to prepare a TiCrSiN coating, the Ti content is 18.3-32.3 at.%, the Cr content is 3.9-6.4 at.%, the N content is 57.9-59.5 at.%, the O content is 1.4-1.8 at.%, the corresponding Si contents are 0.2, 1.4, 6.7, 11.4 and 17.9 at.%, the coating hardness is 20.6, 25.4, 31.1, 26.2 and 24.2GPa, and the coating hardness is hardThe values are lower, with a Si content of 6.7 at.%, and hardness values of 31.1 GPa.
[2]For example, C.W.Zou, etc. by using unbalanced measurement and control sputtering technique, the Ti and Cr target currents are respectively set to 15A and 10A, the substrate bias voltage is-150V, and N is2The flow ratio of/Ar is 1:1, the temperature of the base material is set to be 300 ℃, the atomic content ratio of Cr/Ti in the coating is 41-42%, and the hardness of the coating is increased from 33.6GPa to 36.8GPa by changing the sputtering current of the Si target (4-12A, the corresponding Si content of the coating is 2.1-9.1 at.%). The maximum hardness value of 36.8GPa is obtained at a Si content of 7 at.%.
[3]For example, D.K. Lee, etc. by using magnetron sputtering technology, the Ti and Cr target currents are respectively 80A and 40A, and the working gas N2The flow ratio of/Ar is 5:2, the base material bias voltage is-100V, the base material temperature is 360 ℃, the quaternary Ti-Cr-Si-N coating with the Si contents of 3 at.%, 8 at.%, 12 at.% and 20 at.% is prepared by changing the Si target current of 0-2.2A, and the super-hardness of 42GPa is obtained only when the Si content is 8 at.%.
The literature [2,3] considers that the Cr/Ti content in the coating has no influence on the microstructure and the performance of the coating, and the Si content is a main factor influencing the mechanical property, so the influence of the change of the Si content on the mechanical property of the coating is emphasized and analyzed in a comparative way. In comparison with the above documents, although the Si element content in document [1] is close to that in documents [2 and 3], the coating in document [1] has a low hardness (20.6 to 31.1GPa), which indicates that the Si element content is an important factor affecting the hardness of the coating, but the influence of the element content is also comprehensively considered. In the above 3 documents, when the coating has the highest hardness, the Si content is concentrated in 6.7 to 8 at.%, but the mechanical properties of the coating at low Si content are not refined; the preparation process of the above 3 documents is to directly deposit the Ti-Cr-Si-N coating on the substrate, and the bonding force between the coating and the substrate is not considered, but in practical application, the bonding force is too low to be easily peeled off and fail.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrahard multilayer nano composite coating, which is in a lower Si content range and can more easily obtain an ultrahard hardness value; the wear rate is low, and the energy loss is reduced; has good toughness.
In order to achieve the above object, according to one aspect of the present invention, the present invention provides the following technical solutions:
a method for preparing an ultrahard multilayer nano composite coating comprises the following steps:
1) performing mirror polishing and ultrasonic cleaning on the substrate;
2) cleaning the surface of the base material by using argon ion etching;
3) depositing a transition Cr layer;
4) depositing a CrN layer;
5) and depositing a CrTiSiN layer.
The invention is further configured to: the method comprises the following steps of 1) performing mirror polishing and ultrasonic cleaning on a base material, specifically, performing mirror polishing on the base material on a metallographic polishing machine, firstly performing rough polishing by using w20 diamond powder and matching with rough polishing canvas, then performing fine polishing by using w2.5 diamond powder and matching with fine polishing flannelette, and performing ultrasonic cleaning in an alcohol solution for 20-30 minutes after the base material is cleaned by fine polishing.
The invention is further configured to: and 2) etching and cleaning the surface of the base material by using argon ions, specifically, respectively installing a Ti target and a Cr target on a direct current target, installing a Si target on a radio frequency target, clamping the base material on a sample table, closing a sealing cover, and pumping to 2.5 multiplied by 10 when the vacuum degree of a deposition chamber is up to 2.5 multiplied by 10-3～3.0×10-3And Pa, bombarding the surface of the base material by using argon ions to clean and remove the dirt for 20-30 minutes.
The invention is further configured to: the flow rate of the argon ions was 20sccm and the substrate bias was-500V.
The invention is further configured to: and 3) depositing the transition Cr layer, specifically, maintaining the working gas pressure of the deposition cavity at 0.10-0.15 Pa, preparing at 180-250 ℃, rotating the substrate at a speed of 5 revolutions per minute, flowing Ar gas at 20sccm, biasing the substrate at-60V, and depositing the transition Cr layer for 10 minutes at a Cr target current of 4A.
The invention is further configured to: and 4) depositing the CrN layer, wherein the pressure of working gas in a deposition cavity is kept at 0.10-0.15 Pa, the preparation temperature is 180-250 ℃, the rotating speed of the substrate is 5 revolutions per minute, the flow rate of Ar is 20sccm, the bias voltage of the substrate is-60V, and a Cr target isCurrent 4A, N2The flow rate was 8sccm and deposition was for 30 minutes.
The invention is further configured to: and 5) depositing the CrTiSiN layer, wherein the pressure of working gas in a deposition cavity is kept at 0.10-0.15 Pa, the preparation temperature is 180-250 ℃, the rotating speed of a base material is 5 revolutions per minute, the flow of Ar gas is 20sccm, the bias voltage of the base material is-60V, the currents of a Cr target and a Ti target are both 4A, the power of a Si target is changed to 400-1200W, and the CrTiSiN composite coating is prepared with the deposition time of 180 minutes.
The invention is further configured to: the thickness of the transition Cr layer is 100-120 nm, the thickness of the CrN layer is 300-320 nm, and the thickness of the CrTiSiN layer is 2.5-3 mu m.
The invention is further configured to: the base material is a hard alloy sample substrate.
Compared with the prior art, the invention has the advantages that: the ultra-hard hardness value can be obtained more easily in a lower Si content range; coating with Al2O3The ball is subjected to a friction experiment, and shows that the ball has a lower wear rate and reduces energy loss; and the nano indentation is carried out, so that no defect occurs, and the toughness is good.
Drawings
FIG. 1 is a flow chart of a method for preparing an ultrahard multilayer nanocomposite coating according to the present invention;
FIG. 2 is a scanning electron microscope image of the cross-sectional morphology of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 1;
FIG. 3 is a nanoindentation morphology of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 1;
FIG. 4 is a scanning electron microscope image of the cross-sectional morphology of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 2;
FIG. 5 is a nanoindentation topography of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 2;
FIG. 6 is an indentation loading unloading curve of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 2;
FIG. 7 is a scanning electron microscope image of the cross-sectional morphology of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 3;
FIG. 8 is a nanoindentation topography of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 3;
FIG. 9 is a schematic view of a Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared by the method of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings.
As shown in fig. 1, the invention provides a method for preparing an ultrahard multilayer nano composite coating, the schematic diagram of the prepared Cr/CrN/CrTiSiN multilayer nano composite coating is shown in fig. 9, the purity of Ti and Cr target materials used in the implementation process is 99.9%, and the purity of Si target materials is 99.99%.
Example 1:
1) performing mirror polishing and ultrasonic cleaning on a substrate: and performing mirror polishing on the hard alloy sample substrate on a metallographic polishing machine, performing rough polishing by using w20 diamond powder and rough polishing canvas, performing fine polishing by using w2.5 diamond powder and fine polishing flannelette, and performing ultrasonic cleaning for 20 minutes in an alcohol solution after the substrate is cleaned by fine polishing.
2) Cleaning the surface of the substrate by argon ion etching: respectively mounting Ti target and Cr target on DC target, mounting Si target on RF target, clamping the substrate on the sample stage, closing the sealing cover, and pumping to 2.5 × 10-3And Pa, bombarding the surface of the base material by using argon ions for cleaning and decontamination for 20 minutes, wherein the flow rate of the argon ions is 20sccm, and the bias voltage of the base material is-500V.
3) Depositing a transition Cr layer: the working gas pressure of the deposition cavity is kept at 0.10Pa, a heating source is not started in the coating deposition process, the preparation temperature is 180 ℃, the rotating speed of the substrate is 5 revolutions per minute, the flow rate of Ar is 20sccm, the bias voltage of the substrate is-60V, the current of a Cr target is 4A, and the deposition of a transitional Cr layer is carried out for 10 minutes.
4) Depositing a CrN layer; the pressure of working gas in the deposition chamber is kept at 0.10Pa, no heating source is started in the coating deposition process, the preparation temperature is 180 ℃, the rotating speed of the substrate is 5 r/min, the flow of Ar is 20sccm, the bias voltage of the substrate is-60V, and the current of Cr target is 4A, N2The flow rate was 8sccm and deposition was for 30 minutes.
5) Depositing a CrTiSiN layer; the working gas pressure of the deposition cavity is kept at 0.10Pa, a heating source is not started in the coating deposition process, the preparation temperature is 180 ℃, the rotating speed of the base material is 5 revolutions per minute, the flow rate of Ar is 20sccm, the bias voltage of the base material is-60V, the currents of the Cr target and the Ti target are both 4A, the power of the Si target is changed to 400W, the CrTiSiN composite coating without element content is prepared, and the deposition time is 180 minutes.
The sectional morphology scanning electron microscope picture of the Cr/CrN/CrTiSiN multilayer nano composite coating prepared in example 1 is shown in FIG. 2,
when the coating prepared in example 1 is mixed with Al2O3The abrasion rate of the ball under the conditions of dry friction, load of 3N and opposite grinding distance of 500 m is 1.75 multiplied by 10-7mm3/Nm。
The nano-indentation morphology of example 1 was tested by scanning electron microscopy, with an indentation depth of 1 μm, as shown in FIG. 3.
The Cr/CrN/CrTiSiN multilayer nano composite coating prepared in the embodiment 1 has the following element contents and mechanical properties: the Cr content was 63.2 at.%, the Ti content was 7.5 at.%, the Si content was 0.2 at.%, the N content was 29.1 at.%, the hardness H was 34.9GPa, and the modulus of elasticity E was 481.3 GPa.
Example 2:
the same materials and methods as those of example 1 were used, which are different from those of example 1 in that, in the step 1) of mirror polishing and ultrasonic cleaning of the substrate, ultrasonic cleaning was carried out for 25 minutes; step 2) cleaning the surface of the substrate by argon ion etching, and pumping the vacuum degree of the deposition chamber to 2.7 multiplied by 10-3Pa, bombarding the surface of the base material by using argon ions to clean and remove dirt for 25 minutes; step 3), in the deposition of the transition Cr layer, the pressure of working gas in a deposition cavity is kept at 0.12Pa, and the preparation temperature is 200 ℃; step 4), in the deposition of the CrN layer, the pressure of working gas in a deposition cavity is kept at 0.12Pa, and the preparation temperature is 200 ℃; and step 5) depositing a CrTiSiN layer, keeping the pressure of working gas of a deposition cavity at 0.12Pa, and changing the power of a Si target to 800W at the preparation temperature of 200 ℃.
The schematic diagram of the Cr/CrN/CrTiSiN multilayer nano composite coating prepared in example 2 is shown, and the sectional morphology thereof is shown in a Scanning Electron Microscope (SEM) picture 4.
When the coating prepared in example 2With Al2O3The abrasion rate of the ball under the conditions of dry friction, load of 3N and opposite abrasion distance of 500 meters is 4.58 multiplied by 10-7mm3/Nm。
The nano indentation morphology of example 2 was tested by using a scanning electron microscope, and the indentation depth was 1 μm, and no crack was found, as shown in fig. 5, and the loading and unloading curve was as shown in fig. 6, and no fluctuation occurred, indicating that no defect occurred in the coating and good toughness occurred during the indenter indentation process.
The Cr/CrN/CrTiSiN multilayer nano composite coating prepared in the embodiment 2 has the following element contents and mechanical properties: the Cr content was 61.5 at.%, the Ti content was 8.3 at.%, the Si content was 2.8 at.%, the N content was 27.3 at.%, the hardness H was 48.3GPa, and the elastic modulus E was 478.8 GPa.
Example 3:
the same materials and methods as those of example 1 were used, which are different from those of example 1 in that, in the step 1) of mirror polishing and ultrasonic cleaning of the substrate, ultrasonic cleaning was performed for 30 minutes; step 2) cleaning the surface of the substrate by argon ion etching, and pumping the vacuum degree of the deposition chamber to 3.0 multiplied by 10-3Pa, bombarding the surface of the base material by using argon ions to clean and remove dirt for 30 minutes; step 3), in the deposition of the transition Cr layer, the pressure of working gas in a deposition cavity is kept at 0.15Pa, and the preparation temperature is 250 ℃; step 4), in the deposition of the CrN layer, the pressure of working gas in a deposition cavity is kept at 0.15Pa, and the preparation temperature is 250 ℃; and 5) in the deposition of the CrTiSiN layer, keeping the pressure of working gas of a deposition cavity at 0.15Pa, keeping the preparation temperature at 250 ℃, and changing the power of a Si target to 1200W.
The scanning electron microscope image of the section morphology of the Cr/CrN/CrTiSiN multilayer nanocomposite coating prepared in example 3 is shown in FIG. 7.
When the coating prepared in example 3 is mixed with Al2O3The abrasion rate of the ball under the conditions of dry friction, load of 3N and grinding distance of 500 m is 2.65 multiplied by 10-7mm3/Nm。
The nano-indentation morphology of example 3 was tested by scanning electron microscopy, with an indentation depth of 1 μm, as shown in FIG. 8.
The Cr/CrN/CrTiSiN multilayer nano composite coating prepared in the embodiment 3 has the following element contents and mechanical properties: the Cr content was 60.3 at.%, the Ti content was 8.4 at.%, the Si content was 4.6 at.%, the N content was 26.7 at.%, the hardness H was 46.1GPa, and the modulus of elasticity E was 455.3 GPa.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the superhard multilayer nano composite coating is characterized by comprising the following steps:
1) performing mirror polishing and ultrasonic cleaning on the substrate;
2) cleaning the surface of the base material by using argon ion etching;
3) depositing a transition Cr layer;
4) depositing a CrN layer;
5) and depositing a CrTiSiN layer.
2. The method for preparing the superhard multi-layer nanocomposite coating according to claim 1, wherein the method comprises the following steps: the method comprises the following steps of 1) performing mirror polishing and ultrasonic cleaning on a base material, specifically, performing mirror polishing on the base material on a metallographic polishing machine, firstly performing rough polishing by using w20 diamond powder and matching with rough polishing canvas, then performing fine polishing by using w2.5 diamond powder and matching with fine polishing flannelette, and performing ultrasonic cleaning in an alcohol solution for 20-30 minutes after the base material is cleaned by fine polishing.
3. The method for preparing the superhard multi-layer nanocomposite coating according to claim 1, wherein the method comprises the following steps: and 2) etching and cleaning the surface of the base material by using argon ions, specifically, respectively installing a Ti target and a Cr target on a direct current target, installing a Si target on a radio frequency target, clamping the base material on a sample table, closing a sealing cover, and pumping to 2.5 multiplied by 10 when the vacuum degree of a deposition chamber is up to 2.5 multiplied by 10-3～3.0×10-3And Pa, bombarding the surface of the base material by using argon ions to clean and remove the dirt for 20-30 minutes.
4. The method for preparing the superhard multi-layer nanocomposite coating according to claim 3, wherein the method comprises the following steps: the flow rate of the argon ions was 20sccm and the substrate bias was-500V.
5. The method for preparing the superhard multi-layer nanocomposite coating according to claim 3, wherein the method comprises the following steps: and 3) depositing the transition Cr layer, specifically, maintaining the working gas pressure of the deposition cavity at 0.10-0.15 Pa, preparing at 180-250 ℃, rotating the substrate at a speed of 5 revolutions per minute, flowing Ar gas at 20sccm, biasing the substrate at-60V, and depositing the transition Cr layer for 10 minutes at a Cr target current of 4A.
6. The method for preparing the superhard multi-layer nanocomposite coating according to claim 5, wherein the method comprises the following steps: and 4) depositing the CrN layer, wherein the pressure of working gas in a deposition cavity is kept at 0.10-0.15 Pa, the preparation temperature is 180-250 ℃, the rotating speed of the substrate is 5 revolutions per minute, the flow rate of Ar is 20sccm, the bias voltage of the substrate is-60V, and the Cr target current is 4A, N2The flow rate was 8sccm and deposition was for 30 minutes.
7. The method for preparing the superhard multi-layer nanocomposite coating according to claim 6, wherein the method comprises the following steps: and 5) depositing the CrTiSiN layer, wherein the pressure of working gas in a deposition cavity is kept at 0.10-0.15 Pa, the preparation temperature is 180-250 ℃, the rotating speed of a base material is 5 revolutions per minute, the flow of Ar gas is 20sccm, the bias voltage of the base material is-60V, the currents of a Cr target and a Ti target are both 4A, the power of a Si target is changed to 400-1200W, and the CrTiSiN composite coating is prepared with the deposition time of 180 minutes.
8. The method for preparing the superhard multi-layer nanocomposite coating according to claim 1, wherein the method comprises the following steps: the thickness of the transition Cr layer is 100-120 nm, the thickness of the CrN layer is 300-320 nm, and the thickness of the CrTiSiN layer is 2.5-3 mu m.
9. The method for preparing the superhard multi-layer nanocomposite coating according to claim 1, wherein the method comprises the following steps: the base material is a hard alloy sample substrate.
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