CN111676448A - Preparation method of decoating TiAlCrN nano composite coating - Google Patents
Preparation method of decoating TiAlCrN nano composite coating Download PDFInfo
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- CN111676448A CN111676448A CN202010539668.9A CN202010539668A CN111676448A CN 111676448 A CN111676448 A CN 111676448A CN 202010539668 A CN202010539668 A CN 202010539668A CN 111676448 A CN111676448 A CN 111676448A
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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
- C23C14/0021—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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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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
Abstract
The invention discloses a decodability TiAlCrN nano composite coating, which comprises the following components: the AlCrN base layer, the TiAlCrN multi-element mixed layer and the separation layer are provided with micropores, the TiAlCrN multi-element mixed layer is coated on the AlCrN base layer, the separation layer is coated on the TiAlCrN multi-element mixed layer, the TiAlCrN multi-element mixed layer and the separation layer are used as a modulation period coating, and the AlCrN base layer is coated with a plurality of modulation period coatings in a circulating manner to form a TiAlCrN multi-layer composite structure coating; the invention can realize the effective de-coating of the TiAlCrN coating.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a decoating TiAlCrN nano composite coating and a preparation method thereof.
Background
With the advance of industrial technology, the requirements for coating properties in the field of molds and tools are becoming higher and higher. The technology of coating one or more layers of hard protective films on the surfaces of tools and dies by PVD or CVD has been widely used, such as the common TiCN, TiAlN, CrN, AlCrN, etc. However, the above conventional coating is not sufficient in some cases such as high temperature, high impact strength, and high abrasion. Therefore, researchers have developed quaternary or higher coatings in succession, and the coatings are continuously optimized in structure and composition to obtain better performances such as wear resistance, wear reduction, impact toughness and the like.
Taking TiAlCrN as an example, a target material containing one or two of Ti, Al and Cr elements is generally adopted to deposit the nano composite structure coating, the obtained TiAlCrN coating has extremely high hardness and wear-resistant effect, and different designs of a priming layer and a transition layer are added for improving the film-substrate binding force and impact toughness of the coating. According to the feedback of literature expression and practical application, the TiAlCrN coating has excellent performance, and especially has incomparable effect compared with other coatings in high-strength stamping occasions.
However, many dies and high speed steel tools involve the problem of coping and repeated coating utilization, and when the dies reach a certain life or wear, the coating needs to be removed and recoated by coping and polishing again. The traditional TiCN, TiAlN, CrN, AlCrN and the like coatings are characterized by simple element composition, the coating components are mainly binary or ternary, and the decoating can be realized by adopting the technologies of chemical soaking, electrolysis and the like, for example, TiCN, TiAlN can be decoated by hydrogen peroxide, and AlCrN can be decoated by ferricyanide. The TiAlCrN coating has excellent physical properties and is suitable for most hard protection occasions, but the TiAlCrN coating belongs to a coating which is not easy to fade, is disposable, has no quick and effective solution for fading of three metal mixed nitride coatings in the TiAlCrN at present, and limits the application range of the TiAlCrN coating in the fields of dies, high-speed steel tools and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a decoating TiAlCrN nano composite coating and a preparation method thereof, which can realize effective decoating of the TiAlCrN coating.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a decodability TiAlCrN nanocomposite coating comprising: the AlCrN base layer, the TiAlCrN multi-element mixed layer and the separation layer are provided with micropores, the TiAlCrN multi-element mixed layer is coated on the AlCrN base layer, the separation layer is coated on the TiAlCrN multi-element mixed layer, the TiAlCrN multi-element mixed layer and the separation layer are used as a modulation period coating, and the TiAlCrN multi-element mixed layer and the separation layer are coated on the AlCrN base layer in a circulating mode to form the TiAlCrN multi-layer composite structure coating.
The invention provides a decodability TiAlCrN nano composite coating and a preparation method thereof, which can realize effective decodability of the TiAlCrN coating.
On the basis of the technical scheme, the invention can be further improved as follows:
preferably, the separation layer is an AlCrN separation layer or a CrN separation layer.
As a preferable scheme, the TiAlCrN multi-element mixed layer is obtained by depositing any one or combination of a TiAl + Cr target, a TiAl + CrAl target, a TiAl + TiCr target or a Ti + AlCr target.
Preferably, the method comprises the following steps: the CrN bonding layer is arranged between the AlCrN base layer and the base material to be coated and is provided with micropores.
Preferably, a surface layer is coated on one side, away from the CrN bonding layer, of the TiAlCrN multilayer composite structure coating, the surface layer is provided with micropores, and the surface layer is a CrN surface layer or an AlCrN surface layer.
Preferably, the hardness of the TiAlCrN multilayer composite structure coating is more than 3500HV, and the thickness of the TiAlCrN multilayer composite structure coating is 1-10 μm.
Preferably, the pores have a diameter of 0.1 to 10 μm.
Preferably, the content of aluminum in the AlCrN base layer is less than or equal to 70 at%, and the thickness of the AlCrN base layer is 300-1000 nm.
Preferably, the content of aluminum in the separation layer is less than or equal to 70 at%, and the thickness ratio of the separation layer to the thickness of the TiAlCrN multi-element mixed layer is more than or equal to 1: 1.
As a preferred scheme, the preparation method of the decodability TiAlCrN nano composite coating comprises the following preparation steps:
s1, coating a CrN bonding layer on the surface of the base material;
s2, coating an AlCrN basic layer on the CrN bonding layer;
s3, coating a TiAlCrN multi-element mixed layer on the AlCrN base layer;
s4, coating a separating layer on the TiAlCrN multi-component mixed layer;
s5, taking the TiAlCrN multi-element mixed layer and the separating layer as a modulation period coating, and forming a TiAlCrN multi-layer composite structure coating after a plurality of modulation period coatings are circularly coated on the AlCrN base layer;
s6, coating a CrN surface layer or an AlCrN surface layer on one side of the TiAlCrN multilayer composite structure coating layer, which is far away from the CrN bonding layer.
Drawings
FIG. 1 is a structural diagram of a decodability TiAlCrN nanocomposite coating provided by an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of a decodability TiAlCrN nanocomposite coating provided by an embodiment of the present invention;
wherein: 1. the material comprises a base material, 2 parts of a CrN bonding layer, 3 parts of an AlCrN base layer, 4-1 parts of a TiAlCrN multi-element mixing layer, 4-2 parts of a separating layer, 5 parts of a surface layer and 6 parts of micropores.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Unless otherwise specified, the reagents used in the following examples are commercially available from normal sources.
In order to achieve the purpose of the present invention, as shown in fig. 1-2, the present invention provides a decodability TiAlCrN nanocomposite coating, comprising: the composite coating comprises an AlCrN base layer 3, a TiAlCrN multi-element mixing layer 4-1 and a separating layer 4-2, wherein the AlCrN base layer 3, the TiAlCrN multi-element mixing layer 4-1 and the separating layer 4-2 are provided with micropores, the TiAlCrN multi-element mixing layer 4-1 is coated on the AlCrN base layer 3, the separating layer 4-2 is coated on the TiAlCrN multi-element mixing layer 4-1, the TiAlCrN multi-element mixing layer 4-1 and the separating layer 4-2 are used as a modulation period coating, and the AlCrN base layer 3 is coated with a plurality of modulation period coatings in a circulating mode to form the TiAlCrN multi-layer composite structure coating.
The plurality of modulation period coatings can be preferably 1-20 modulation period coatings, and each modulation period coating is 50-500nm in thickness.
The total thickness of the TiAlCrN multilayer composite structure coating is 1-10 mu m.
The prepared TiAlCrN multilayer composite structure coating can be decoiled by adopting a decoiling process of a conventional AlCrN coating, has a good decoiling effect, and can be stripped.
The embodiment provides a removable TiAlCrN nano composite coating and a preparation method thereof, which can realize effective removal of the TiAlCrN coating.
In some embodiments, the spacer layer 4-2 is an AlCrN spacer layer or a CrN spacer layer.
By adopting the embodiment, the AlCrN coating or the CrN coating is used as the separation layer 4-2, the TiAlCrN multi-component mixing layers 4-1 are separated to form discontinuous functional films, although the TiAlCrN multi-component mixing layer 4-1 is not easy to chemically react with the depainting agent, the separation layer 4-2 existing between the TiAlCrN multi-component mixing layers 4-1 can rapidly leak the depainting agent through the micropores 6 to carry out chemical reaction to obtain water-soluble substances, and then the TiAlCrN multi-component mixing layer 4-1 which cannot be dissolved at the upper layer is rapidly stripped through water, and the chemical reaction can be circulated until the TiAlCrN multi-component mixing layer coating is completely stripped through water.
The thickness of the TiAlCrN multi-element mixed layer 4-1 is 25-200 nm.
In some embodiments, the TiAlCrN multi-element mixed layer 4-1 is deposited by any one or any combination of a TiAl + Cr target, a TiAl + CrAl target, a TiAl + TiCr target or a Ti + AlCr target.
The thickness of the TiAlCrN multi-element mixed layer 4-1 is 25-200 nm.
In some embodiments, the method comprises: the CrN bonding layer 2 is arranged between the AlCrN base layer 3 and the base material 1 to be coated, and the CrN bonding layer 2 is provided with micropores 6.
The CrN bonding layer 2 can enhance the bonding effect.
In some embodiments, a surface layer 5 is coated on the side of the TiAlCrN multilayer composite structure coating far away from the CrN bonding layer 2, the surface layer 5 has micropores, and the surface layer 5 is a CrN surface layer or an AlCrN surface layer.
In some embodiments, the TiAlCrN multilayer composite coating has a hardness greater than 3500HV and a thickness of 1-10 μm.
The hardness of the nano AlCrN multilayer composite structure coating is greater than 3500HV, and the nano AlCrN multilayer composite structure coating has excellent wear-resistant effect.
In some embodiments, the pores 6 have a pore diameter of 0.1 to 10 μm, and the pores 6 preferably have a pore diameter of 0.5 to 5 μm.
In some embodiments, the AlCrN base layer 3 has an aluminum content of 70 at% or less, and the AlCrN base layer 3 has a thickness of 300-1000 nm.
The 3 degree of the AlCrN base layer is less than 3000 HV.
In some embodiments, the aluminum content in the separation layer 4-2 is less than or equal to 70 at%, and the ratio of the thickness of the separation layer 4-2 to the thickness of the TiAlCrN multi-element mixed layer 4-1 is greater than or equal to 1: 1.
In some embodiments, a preparation method of a decodability TiAlCrN nano composite coating comprises the following preparation steps:
s1, coating a CrN bonding layer 2 on the surface of a base material;
s2 coating an AlCrN basic layer 3 on the CrN bonding layer 2;
s3, coating a TiAlCrN multi-element mixed layer 4-1 on the AlCrN base layer 3;
s4, coating a separating layer 4-2 on the TiAlCrN multi-element mixed layer 4-1;
s5, taking the TiAlCrN multi-element mixed layer 4-1 and the separating layer 4-2 as a modulation period coating, and forming a TiAlCrN multi-layer composite structure coating after a plurality of modulation period coatings are circularly coated on the AlCrN base layer 3;
s6, coating a CrN surface layer or an AlCrN surface layer on one side of the TiAlCrN multilayer composite structure coating layer, which is far away from the CrN bonding layer.
The substrate is preferably a hob, a mould or other substrate.
And (3) loading the high-speed steel hob after deburring and cleaning into a coating machine, heating to 450 ℃, vacuumizing to be below 5e-4mBar, and etching for 30 minutes by adopting Ar ions. Firstly, introducing nitrogen into a cavity of a coating machine, then opening a metal chromium target, and applying 50V bias voltage to coat a 300nm CrN bonding layer on the upper surface of a hob; closing the metal chromium target, starting the AlCr target material (50/50 at%), and continuously coating an AlCrN base layer with the thickness of 1000 nm; then starting a TiAl target material (50/50 at%) at the same time, and depositing a TiAlCrN multi-component mixed layer with the thickness of 50 nm; closing the TiAl target material after the thickness set value is reached, and only depositing an AlCrN separation layer with the thickness of 100 nm; starting the TiAl target again after the thickness set value is reached, depositing a TiAlCrN composite layer with the thickness of 50nm, and circulating for 10 times in total to obtain a TiAlCrN multilayer composite structure coating with the thickness of 1500 nm; and finally, coating an AlCrN monolayer with the thickness of 200nm on the surface layer to obtain a coating with the total thickness of 3.0 mu m and the color of black and gray. The coating prepared by the method has better film-substrate binding force compared with the common TiAlCrN coating, can meet the dry cutting and wet cutting occasions of a hob, can prolong the service life by 30-40 percent compared with the common TiAlCrN coating, can realize complete decoating by adopting the conventional AlCrN layer decoating process, and can not generate corrosion on a high-speed steel substrate.
The polished mould was cleaned and loaded into a coater, heated to 450 ℃ and evacuated to a vacuum below 5e-4mBar and etched with Ar ions for 30 minutes. Firstly, introducing nitrogen into a cavity of a coating machine, then starting an AlCr target (40/60 at%), and applying 70V bias voltage to coat an AlCrN base layer with the thickness of 1000nm on a mould; then starting a TiAl target material (50/50 at%) at the same time, and depositing a TiAlCrN multi-element mixed layer with the thickness of 100 nm; closing the TiAl target material after the thickness set value is reached, and only depositing an AlCrN separation layer with the thickness of 150 nm; starting the TiAl target again after the thickness set value is reached, depositing the TiAlCrN multilayer composite structure coating with the thickness of 100nm, and circulating the steps for 8 times so as to obtain the TiAlCrN multilayer composite structure coating with the thickness of 2000 nm; and finally, coating a CrN surface layer with the thickness of 500nm on the surface to obtain a CrN composite material with the total thickness of 3.5 mu m and silvery white color. The coating prepared by the method has better toughness and impact resistance than the common TiAlCrN coating, the hardness of the coating can reach more than 3600HV, the complete de-coating can be realized by adopting the common AlCrN de-coating process, and the steel matrix of the die can not be corroded.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A decodability TiAlCrN nano composite coating is characterized by comprising the following components: the AlCrN base layer, the TiAlCrN multi-element mixed layer and the separation layer are provided with micropores, the TiAlCrN multi-element mixed layer is coated on the AlCrN base layer, the separation layer is coated on the TiAlCrN multi-element mixed layer, the TiAlCrN multi-element mixed layer and the separation layer are used as a modulation period coating, and the TiAlCrN multi-element mixed layer and the separation layer are coated on the AlCrN base layer in a circulating mode to form the TiAlCrN multi-layer composite structure coating.
2. The decodabie TiAlTiCrN nanocomposite coating of claim 1 wherein said spacer layer is an AlCrN spacer layer or a CrN spacer layer.
3. The decodabie TiAlCrN nanocomposite coating according to claim 1, wherein the TiAlCrN multi-component mixed layer is deposited from any one or a combination of TiAl + Cr target, TiAl + CrAl target, TiAl + TiCr target or Ti + AlCr target.
4. The decodabie TiAlCrN nanocomposite coating according to claim 1, comprising: the CrN bonding layer is arranged between the AlCrN base layer and the base material to be coated and is provided with micropores.
5. The decodable TiAlCrN nanocomposite coating according to claim 4, wherein a surface layer is coated on the side of the TiAlCrN multilayer composite structure coating away from the CrN bonding layer, the surface layer is provided with micropores, and the surface layer is a CrN surface layer or an AlCrN surface layer.
6. The decodabie TiAlCrN nanocomposite coating according to claim 1, wherein the TiAlCrN multilayer composite structure coating has a hardness of greater than 3500HV and a thickness of 1-10 μm.
7. The decodabie TiAlCrN nanocomposite coating according to any of claims 1, 4 to 5, characterized in that the pores have a pore diameter of 0.1 to 10 μm.
8. The TiAlCrN nanocomposite coating according to claim 1, wherein the AlCrN base layer has an aluminum content of 70 at% or less, and the AlCrN base layer has a thickness of 300-1000 nm.
9. The decodabie TiAlCrN nanocomposite coating according to claim 1, wherein the aluminum content in the spacer layer is no greater than 70 at%, and the thickness ratio of the spacer layer to the thickness of the TiAlCrN multicomponent mixed layer is no less than 1: 1.
10. A preparation method of a decodability TiAlCrN nano composite coating is characterized by comprising the following preparation steps:
s1, coating a CrN bonding layer on the surface of the base material;
s2, coating an AlCrN basic layer on the CrN bonding layer;
s3, coating a TiAlCrN multi-element mixed layer on the AlCrN base layer;
s4, coating a separating layer on the TiAlCrN multi-component mixed layer;
s5, taking the TiAlCrN multi-element mixed layer and the separating layer as a modulation period coating, and forming a TiAlCrN multi-layer composite structure coating after a plurality of modulation period coatings are circularly coated on the AlCrN base layer;
s6, coating a CrN surface layer or an AlCrN surface layer on one side of the TiAlCrN multilayer composite structure coating layer, which is far away from the CrN bonding layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774857A (en) * | 2022-03-18 | 2022-07-22 | 上海应用技术大学 | TiAlCrN micro-nano coating and preparation method thereof |
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Application publication date: 20200918 |
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