阅读说明：本技术 AlCrSiN/AlCrN/AlCrON/AlCrN多层纳米复合涂层的制备工艺 (Preparation process of AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating ) 是由 王铁钢 林伟 刘迁 刘艳梅 阎兵 彭勇 于 2020-06-10 设计创作，主要内容包括：本发明公开了一种AlCrSiN/AlCrN/AlCrON/AlCrN多层纳米复合涂层的制备工艺,属于复合涂层制备技术领域。该工艺采用电弧离子镀膜技术镀膜,靶材选取金属Cr靶、AlCr靶、AlCrSi靶。镀膜前先通入氩气辉光放电清洗,随后开启Cr靶对基体表面进行离子轰击清洗,然后沉积CrN过渡层,最后通入氮气和氧气作为反应气体,交替开启AlCrSi靶和AlCr靶,依次往复沉积AlCrSiN层、AlCrN层、AlCrON层和AlCrN层。本发明制备的多层纳米复合涂层工艺简单,涂层组织结构致密、涂层与基体间结合力强,具有较高的硬度和强度,良好的耐磨损性能。(The invention discloses a preparation process of an AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating, belonging to the technical field of composite coating preparation. The process adopts an arc ion plating technology to plate the film, and the target material is selected from a metal Cr target, an AlCr target and an AlCrSi target. Before coating, argon is firstly introduced for glow discharge cleaning, then a Cr target is started for ion bombardment cleaning on the surface of a substrate, then a CrN transition layer is deposited, finally nitrogen and oxygen are introduced as reaction gases, an AlCrSi target and an AlCr target are alternately started, and an AlCrSiN layer, an AlCrN layer, an AlCrON layer and an AlCrN layer are sequentially and repeatedly deposited. The multilayer nano composite coating prepared by the invention has the advantages of simple process, compact coating tissue structure, strong binding force between the coating and a substrate, higher hardness and strength and good wear resistance.)

1. A preparation process of AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is characterized by comprising the following steps: the process comprises the steps of firstly depositing a CrN transition layer on a substrate by adopting an arc ion coating technology, and then sequentially depositing an AlCrSiN layer, an AlCrN layer, an AlCrON layer and an AlCrN layer on the CrN transition layer in a reciprocating mode, so that the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is obtained.

2. The process of preparing AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating of claim 1, wherein: in the process, the target material is selected from a pure metal Cr target, an AlCr alloy target and an AlCrSi alloy target, and the purity of the target material is 99.9 wt%; when each layer is deposited, the arc current is set to be 60-100A.

3. The process of preparing the multilayer nanocomposite coating of AlCrSiN/AlCrN/AlCrON according to claim 2, wherein: the process comprises the following steps:

(1) placing the pretreated substrate on a central rotating stand of a coating chamber, and pumping the vacuum chamber to 3.0 × 10^-3Pa below;

(2) firstly, carrying out glow discharge cleaning on a substrate, and then depositing a CrN transition layer with the thickness of 100-300 nm on the surface of the substrate to improve the binding force between a working layer and the substrate;

(3) depositing a multi-layer composite coating: firstly, starting an AlCrSi alloy target, introducing argon and nitrogen, and depositing an AlCrSiN layer; then only starting an AlCr target, introducing argon and nitrogen, and depositing an AlCrN layer; then introducing oxygen to deposit an AlCrON layer; finally, closing the oxygen valve, only introducing argon and nitrogen, and depositing an AlCrN layer;

(4) and (4) repeating the process of the step (3) for multiple times, and setting different modulation periods and deposition times of the coating according to the total thickness of the required coating to obtain the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating.

4. The process of claim 3, wherein the multilayer nanocomposite coating comprises AlCrSiN/AlCrN/AlCrON/AlCrN: the glow discharge cleaning process in the step (2) comprises the following steps: firstly, cleaning a substrate by adopting high-pulse negative bias glow discharge for 10-30 min, starting a Cr target after glow cleaning, and respectively carrying out ion bombardment cleaning on the surface of the substrate for 2min by sequentially adjusting pulse bias to-800V, -600V, -400V and-200V.

5. The process of preparing AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating of claim 4, wherein: the glow discharge cleaning process in the step (2) comprises the following steps: heating the furnace chamber to 400-500 ℃, introducing argon gas of 300-500 sccm, setting pulse bias voltage of-600-1000V, and performing glow discharge cleaning on the substrate; the ion bombardment cleaning process comprises the following steps: after glow discharge cleaning, starting the Cr target, adjusting the argon flow to be 50-150 sccm, and sequentially cleaning for 2min under the pulse negative bias conditions of-800V, -600V, -400V and-200V.

6. The process of claim 3, wherein the multilayer nanocomposite coating comprises AlCrSiN/AlCrN/AlCrON/AlCrN: the process of depositing the CrN transition layer in the step (2) is as follows: after glow discharge and ion bombardment cleaning, setting pulse bias voltage to be-60 to-100V, duty ratio to be 60 to 90 percent, starting a Cr target, introducing argon gas flow to be 50sccm and nitrogen gas flow to be 200sccm, adjusting the deposition pressure to be 0.5 to 1.2Pa, and depositing a CrN transition layer for 10 to 30 min.

7. The process of claim 3, wherein the multilayer nanocomposite coating comprises AlCrSiN/AlCrN/AlCrON/AlCrN: when the AlCrSiN layer is deposited in the step (3), setting pulse bias voltage of-70V to-120V, duty ratio of 60% to 90%, and introducing argon and nitrogen to keep deposition pressure of 0.8 Pa to 1.3 Pa; when an AlCrN layer is deposited, setting a pulse bias voltage of-80 to-100V, setting the duty ratio of 60 to 90 percent, and introducing argon and nitrogen to adjust the deposition pressure to 1.5 to 3 Pa; when the AlCrON layer is deposited, setting pulse bias voltage of-80 to-100V, duty ratio of 60 to 90 percent, and introducing argon, oxygen and nitrogen to keep deposition pressure of 2 to 3 Pa.

8. The process of preparing AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating according to claim 3 or 7, wherein: when the AlCrSiN coating and the AlCrN coating are deposited in the step (3), the flow of argon is 50sccm, the flow of nitrogen is 600sccm, and the total flow is 650 sccm; when the AlCrON coating is deposited, the flow of argon is 50sccm, the flow of nitrogen is 600sccm, the flow of oxygen is 20sccm, and the total flow is 670 sccm.

9. The process of preparing AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating of claim 1, wherein: the matrix is metal or hard alloy, the prepared AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is formed by sequentially overlapping an AlCrSiN layer, an AlCrN layer, an AlCrON layer and an AlCrN layer into a period, the modulation period of the coating is 50-800nm, the period number is more than or equal to 4, and the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 3:1:1:1, the total thickness of the deposited coating is controlled to be 3 μm.

10. The process of preparing AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating of claim 1, wherein: the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is formed by embedding nanocrystals with a face-centered cubic structure in an amorphous layer, a low-hardness hexagonal phase is not generated, and the coating preferentially grows along a (110) crystal face and a (200) crystal face of (Cr, Al) N.

Technical Field

The invention relates to the technical field of preparation of multi-element nano composite coatings, in particular to a preparation process of an AlCrSiN/AlCrN/AlCrON/AlCrN multi-layer nano composite coating.

Background

With the development of low-temperature and low-pressure vapor deposition technology, films which do not exist in an equilibrium state can be deposited in a non-equilibrium state by utilizing magnetron sputtering, arc ion plating and PECVD (plasma enhanced chemical vapor deposition), and particularly, the generation of auxiliary deposition technologies such as plasma, ion beam and the like can be used for synthesizing high-quality coatings at lower temperature, so that the development of hard coatings is greatly promoted. In recent years, the bonding strength between the coating and the substrate, the strength, hardness, toughness, oxidation resistance, high temperature resistance, wear resistance and other properties of the cutter coating are improved, the application of the coated cutter in dry cutting machining can be widened, and the requirements of high-speed cutting of difficult-to-machine materials and the requirements of speed, feed rate, reliability, wear resistance and good cutting controllability required by modern metal machining are met. The vacuum vapor deposition technology of the coating is continuously updated, the cutter coating is developed into a multi-layer composite, gradient coating and nano composite structure from an initial single layer, and a mixed composite structure coating is newly developed recently.

In order to develop a multilayer nano composite coating with compact structure, high hardness and high wear resistance, the patent adopts an arc ion plating technology to deposit an AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating on a metal or alloy matrix, thereby further improving the mechanical property of a coated cutter and prolonging the service life.

Disclosure of Invention

The invention aims to provide a preparation process of an AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating, and the prepared AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating has high hardness, high wear resistance and high thermal stability.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a process for preparing the multi-layer nano composite AlCrSiN/AlCrN/AlCrON/AlCrN coating includes such steps as depositing CrN transition layer on substrate by arc ion plating, and depositing AlCrSiN layer, AlCrN layer, AlCrON layer and AlCrN layer in turn.

In the process, the target material is selected from a pure metal Cr target, an AlCr alloy target and an AlCrSi alloy target, and the purity of the target material is 99.9 wt%; when each layer is deposited, the arc current is set to be 60-100A.

The process specifically comprises the following steps:

(1) placing the pretreated substrate on a central rotating stand of a coating chamber, and pumping the vacuum chamber to 3.0 × 10^-3Pa below;

(2) firstly, carrying out glow discharge cleaning on a substrate, and then depositing a CrN transition layer with the thickness of 100-300 nm on the surface of the substrate to improve the binding force between a working layer and the substrate;

(3) depositing a multi-layer composite coating: firstly, starting an AlCrSi alloy target, introducing argon and nitrogen, and depositing an AlCrSiN layer; then only starting an AlCr target, introducing argon and nitrogen, and depositing an AlCrN layer; then introducing oxygen to deposit an AlCrON layer; finally stopping introducing oxygen, introducing only argon and nitrogen, and depositing an AlCrN layer;

(4) and (4) repeating the process of the step (3) for multiple times, and setting different modulation periods and deposition times of the coating according to the total thickness of the required coating to obtain the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating.

The glow discharge cleaning process in the step (2) comprises the following steps: firstly, cleaning a substrate by adopting high-pulse negative bias glow discharge for 10-30 min, starting a Cr target after glow cleaning, and adjusting pulse bias to-800V, -600V, -400V and-200V in sequence to respectively perform ion bombardment cleaning on the surface of the substrate for 2 min.

In the step (2), the specific process of glow discharge cleaning is as follows: heating the furnace chamber to 400-500 ℃, introducing argon gas of 300-500 sccm, setting pulse bias voltage of-600-1000V, and performing glow discharge cleaning on the substrate; the ion bombardment cleaning process comprises the following steps: after glow discharge cleaning, starting the Cr target, adjusting the argon flow to be 50-150 sccm, and sequentially cleaning for 2min under the pulse negative bias conditions of-800V, -600V, -400V and-200V.

In the step (2), the process of depositing the CrN transition layer is as follows: after glow discharge and ion bombardment cleaning, setting pulse bias voltage to be-60 to-100V, duty ratio to be 60 to 90 percent, starting a Cr target, introducing argon gas flow to be 50sccm and nitrogen gas flow to be 200sccm, adjusting deposition pressure to be 0.5 to 1.2Pa, and depositing a CrN transition layer for 10 to 30 min.

In the step (3), when the AlCrSiN layer is deposited, setting pulse bias voltage of-70V to-120V, duty ratio of 60% to 90%, and introducing argon and nitrogen to keep deposition pressure of 0.8 Pa to 1.3 Pa; when an AlCrN layer is deposited, setting a pulse bias voltage of-80 to-100V, setting the duty ratio of 60 to 90 percent, and introducing argon and nitrogen to keep the deposition pressure at 1.5 to 3 Pa; when the AlCrON layer is deposited, setting pulse bias voltage of-80 to-100V, duty ratio of 60 to 90 percent, and introducing argon, oxygen and nitrogen to keep deposition pressure at 2 to 3 Pa.

In the step (3), when the AlCrSiN coating and the AlCrN coating are deposited, argon gas flow is introduced at 50sccm, nitrogen gas flow is 600sccm, and total flow is 650 sccm; when the AlCrON coating is deposited, the flow of argon is 50sccm, the flow of nitrogen is 600sccm, the flow of oxygen is 20sccm, and the total flow is 670 sccm.

The matrix is metal or hard alloy, the prepared AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is formed by sequentially overlapping an AlCrSiN layer, an AlCrN layer, an AlCrON layer and an AlCrN layer into a period, the modulation period of the coating is 50-800nm, the period number is more than or equal to 4, and the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 3:1:1:1, the total thickness of the coating is controlled to be 3 μm.

The AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating is formed by embedding nanocrystals with a face-centered cubic structure in an amorphous layer, a low-hardness hexagonal phase is not generated, and the coating preferentially grows along a (110) crystal face and a (200) crystal face of (Cr, Al) N.

The design mechanism of the invention is as follows:

the invention adds Si element in AlCrN coating, and forms amorphous Si by utilizing the solid solution strengthening effect of Al and Cr elements₃N₄Coating is strengthened by wrapping the composite structure of the nanocrystalline, and in addition, O element is added in the AlCrN coating, and the thermal stability of the AlCrON coating is utilizedThe heat resistance of the coating is improved by the aid of the property and the thermal barrier capability, the AlCrN coating is wrapped by the AlCrN coating with high toughness, and the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer are mutually overlapped and arranged to form a multi-layer nano composite coating, so that the AlCrSiN/AlCrN/AlCrON/AlCrN multi-layer composite coating has excellent characteristics obviously superior to those of a single-layer coating, and working condition requirements of high-speed cutting, dry cutting and the like are met.

The nano multilayer composite coating prepared by the invention is a modulation structure, namely, has a certain repetition period. Three different coatings are alternately deposited in a nanoscale size, the obtained multilayer nano composite structure has a superhard phenomenon that the hardness is abnormally increased, the advantages of different materials are gathered, the defects of a single-layer film are overcome, and the high hardness, the high toughness and the excellent wear resistance of the coatings are realized.

The invention has the following advantages:

1. the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating developed by the invention has higher hardness and toughness, low friction coefficient and good wear resistance.

2. The AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating developed by the invention has good high-temperature thermal stability and corrosion resistance, and can be used in the field of high-speed dry cutting processing.

3. The AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating developed by the invention has uniform thickness, compact structure and good bonding strength with a substrate.

4. The AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating developed by the invention has good repeatability of the preparation process, wide application range and very strong practicability.

Drawings

FIG. 1 is a diffraction pattern of AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coating prepared by arc ion plating; wherein: (a) the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 5:1:1: 1; (b) the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 4:1:1: 1; (c) the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 3:1:1: 1; (d) the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 2:1:1: 1; (e) the modulation ratio of the AlCrSiN layer, the AlCrN layer, the AlCrON layer and the AlCrN layer is 1:3:3: 3.

FIG. 2 is a surface topography of the AlCrSiN/AlCrN/AlCrON/AlCrN nanocomposite coating prepared by the arc ion plating technique.

FIG. 3 is a cross-sectional view of the AlCrSiN/AlCrN/AlCrON/AlCrN nanocomposite coating prepared by the arc ion plating technique.

FIG. 4 is a nano indentation test curve of AlCrSiN/AlCrN/AlCrON/AlCrN multi-layer nano composite coating prepared by arc ion plating.

FIG. 5 shows the shape of the multilayer nano composite coating of AlCrSiN/AlCrN/AlCrON/AlCrN prepared by the arc ion plating technique after scratch test.

FIG. 6 is a friction coefficient test curve of AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coatings prepared by arc ion plating.

Detailed Description

The present invention will be described in further detail by way of examples.

In the following examples, a full-automatic arc ion plating machine, model V-TECH AIP 650/750, produced by Dalianwei Ticke technologies, Inc., was used to deposit AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nanocomposite coatings on substrates.

In the process of depositing the multilayer nano composite coating, the substrate is metal or hard alloy, and the target material is selected from pure metal Cr target, AlCr alloy target and AlCrSi alloy target; when the multilayer nano composite coating is deposited, the Cr target is firstly started, then the AlCrSi target and the AlCr target are alternately started to deposit corresponding AlCrSiN layer, AlCrN layer and AlCrON layer, the deposition pressure of each layer, the flow of introduced gas and the arc current parameter of each target are respectively controlled, and the AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating which is formed by sequentially and repeatedly superposing the AlCrSiN layer, the AlCrN layer and the AlCrN layer is prepared on the substrate.