CN111500982A - Tetrahedral amorphous carbon composite coating and preparation method thereof - Google Patents

Tetrahedral amorphous carbon composite coating and preparation method thereof Download PDF

Info

Publication number
CN111500982A
CN111500982A CN202010390073.1A CN202010390073A CN111500982A CN 111500982 A CN111500982 A CN 111500982A CN 202010390073 A CN202010390073 A CN 202010390073A CN 111500982 A CN111500982 A CN 111500982A
Authority
CN
China
Prior art keywords
film
tetrahedral amorphous
amorphous carbon
composite coating
carbon composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010390073.1A
Other languages
Chinese (zh)
Other versions
CN111500982B (en
Inventor
毛昌海
祖全先
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arison Surface Technology Suzhou Co Ltd
Original Assignee
Arison Surface Technology Suzhou Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arison Surface Technology Suzhou Co Ltd filed Critical Arison Surface Technology Suzhou Co Ltd
Priority to CN202010390073.1A priority Critical patent/CN111500982B/en
Publication of CN111500982A publication Critical patent/CN111500982A/en
Application granted granted Critical
Publication of CN111500982B publication Critical patent/CN111500982B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C14/0605—Carbon
    • 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
    • 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
    • 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
    • C23C14/0658—Carbon nitride
    • 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
    • C23C14/3485—Sputtering using pulsed power to the target
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a tetrahedral amorphous carbon composite coating, which comprises: bottom bonding layer: is CNXA film; surface functional layer: is high SP3A tetrahedral amorphous carbon film with carbon-hybridized bond content; an alloy base material is arranged below the bottom binding layer, and a surface functional layer is arranged above the bottom binding layer; the wear-resistant and abrasion-resistant diamond-like carbon film has the advantages of low cost, simple process flow, and remarkably improved film-substrate bonding strength, and has better wear-resistant and abrasion-resistant effects because the film-substrate has higher hardness than other diamond-like carbon films.

Description

Tetrahedral amorphous carbon composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of surface treatment, in particular to a tetrahedral amorphous carbon composite coating and a preparation method thereof.
Background
In nature, carbon exists in the form of stable graphitic states, metastable diamond structures, and hydrocarbon polymers. Wherein the graphite is SP2Carbon hybrid bond formation, diamond with SP3Hybrid bond formation, synthetic diamond-like carbon film comprising two hybrid bonds, a tetrahedral amorphous carbon film having a higher proportion of SPs3The bond has physical characteristics more tending to diamond, mainly reflected in excellent tribological performance, high microhardness, high elastic modulus, high resistance, high heat conduction, excellent photoelectric performance and the like, especially in automobilesThe product has extremely high potential market value and is concerned by the industry of household appliances and electronics.
These tetrahedral amorphous carbon thin films also have significant drawbacks such as extremely high internal stress, low deposition rate, inability to produce thick films, too weak film-to-film bond strength, and the like. In order to meet the application requirements of industrial production, the enhancement of film-substrate bonding effect is preferably considered in the deposition process of the thin film, so as to prevent the failure caused by peeling in the use process. The technical directions for enhancing the film-substrate bonding effect mainly include the following types: 1. the film hardness is reduced, a low-stress film can be obtained, the adhesion effect is improved, but the characteristic of the film diamond-like carbon is reduced; 2. the film thickness is reduced, and the method is only suitable for occasions with small loads; 3. the design of adding a bottom layer or a composite layer structure, such as depositing a tetrahedral amorphous carbon film on the surface based on a metal layer such as titanium, chromium or a hard film, is also the mainstream process of the current research, but the equipment complexity and the cost investment are higher, and the film with the thickness of more than 1 micron is difficult to prepare, and the current scientific research is mainly used, so that the practical application is few particularly in high-load occasions.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a tetrahedral amorphous carbon composite coating and a preparation method thereof, which have the advantages of low cost, simple process flow and obviously improved film-substrate bonding strength, and in addition, the wear-reducing and wear-resisting effects are better because the tetrahedral amorphous carbon composite coating has higher hardness than other diamond-like carbon films.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a tetrahedral amorphous carbon composite coating comprising:
bottom bonding layer: is CNXA film;
surface functional layer: is high SP3A tetrahedral amorphous carbon film with carbon-hybridized bond content;
an alloy base material is arranged below the bottom binding layer, and a surface functional layer is arranged above the bottom binding layer.
The tetrahedral amorphous carbon composite coating and the preparation method thereof provided by the invention have the advantages of low cost, simple process flow, and obviously improved film-substrate bonding strength, and in addition, the wear-reducing and wear-resisting effects are better because the tetrahedral amorphous carbon composite coating has higher hardness than other diamond-like carbon films.
On the basis of the technical scheme, the invention can be further improved as follows:
preferably, the CNXThe atomic percentage of nitrogen element in the film is 1-50%; x is more than 0 and less than or equal to 1.
Preferably, the CNXThe film is a diamond-like carbon film doped with N element, and the CNx film comprises SP3Carbon hybridized bond.
Preferably, the CNXThe film is doped with any one or more of Si, F, H and S elements through process gas.
Preferably, a metal bonding layer is arranged between the bottom bonding layer and the alloy substrate, and the metal bonding layer is a Ti element metal bonding layer or a Cr element metal bonding layer.
Preferably, the CNXThe film is obtained by preparing and depositing a graphite target and nitrogen, and the high SP3The tetrahedral amorphous carbon film with the carbon hybrid bond content is prepared by adopting a physical vapor deposition process through a graphite target and argon, wherein the physical vapor deposition process adopts an electric arc ion plating and high-power pulse magnetron sputtering process.
Preferably, the CNXThe thickness of the film is 50-1000nm, and the SP3The thickness of the tetrahedral amorphous carbon film with carbon hybridization bonds is 100-3000 nm.
Preferably, the hardness of the surface functional layer is more than or equal to 5000HV, and the hardness of the surface functional layer is more than that of the bottom binding layer.
As a preferred scheme, the preparation method of the tetrahedral amorphous carbon composite coating comprises the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate to 100-350 ℃;
2) cleaning the surface of the alloy base material by ion etching;
3) introducing mixed gas of nitrogen and argonTurning on bias power supply and graphite target material to deposit bottom binding layer CNXA film;
4) closing nitrogen, continuously keeping introducing argon, keeping turning on a bias voltage power supply and the graphite target, and depositing the surface functional layer high Sp in the environment of 50-300 DEG C3A tetrahedral amorphous carbon film with carbon hybridized bond content.
Surface functional layer high Sp3The tetrahedral amorphous carbon film with carbon hybridized bond content is preferably deposited in different parameter segments to further reduce the stress in the layer.
As a preferred scheme, the preparation method of the tetrahedral amorphous carbon composite coating comprises the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate to 100-350 ℃;
2) cleaning the surface of the alloy base material by ion etching;
3) introducing mixed gas of nitrogen, argon and acetylene, starting a bias power supply and the graphite target material, and depositing a hydrogen-containing CN (carbon nitride) of the bottom bonding layerXA film;
4) closing nitrogen and acetylene, continuously keeping argon gas introduction, keeping turning on a bias voltage power supply and a graphite target, and depositing a surface functional layer high Sp in an environment with the temperature of 50-300 DEG C3A tetrahedral amorphous carbon film with carbon hybridized bond content.
Surface functional layer high Sp3The tetrahedral amorphous carbon film with carbon hybridized bond content is preferably deposited in different parameter segments to further reduce the stress in the layer.
Drawings
Fig. 1 is a structural diagram of a tetrahedral amorphous carbon composite coating according to an embodiment of the present invention;
wherein: 1. alloy substrate, 2. bottom bonding layer, 3. surface functional layer.
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 object of the present invention, the present invention provides a tetrahedral amorphous carbon composite coating, comprising:
bottom bonding layer 2: is CNXA film;
surface functional layer 3: is high SP3A tetrahedral amorphous carbon film with carbon-hybridized bond content;
an alloy substrate 1 is arranged below the bottom binding layer 2, and a surface functional layer 3 is arranged above the bottom binding layer 2.
The embodiment provides the tetrahedral amorphous carbon composite coating and the preparation method thereof, the cost is low, the process flow is simple, the film-substrate bonding strength is obviously improved, and in addition, the wear-reducing and wear-resisting effects are better and excellent because the tetrahedral amorphous carbon composite coating has higher hardness than other diamond-like carbon films.
In some embodiments, the CNXThe atomic percentage of nitrogen element in the film is 1-50%; x is more than 0 and less than or equal to 1.
In some embodiments, the CNXThe film is a diamond-like carbon film doped with N element, and the CNx film comprises SP3Carbon hybridized bond.
In some embodiments, the CNXThe film can be selectively doped with any one or more of Si, F, H and S elements through process gas.
In some embodiments, a metal bonding layer may be optionally disposed between the bottom bonding layer 2 and the alloy substrate 1, and the metal bonding layer is a Ti metal bonding layer or a Cr metal bonding layer.
In some embodiments, the CNXThe film is obtained by preparing and depositing a graphite target and nitrogen, and the high SP3The tetrahedral amorphous carbon film with carbon hybrid bond content is prepared by adopting a physical vapor deposition process through a graphite target and argon, wherein the physical vapor deposition process adopts arc ion plating and high powerAnd (3) a pulse magnetron sputtering process.
In some embodiments, the CNXThe film thickness is 50-1000nm, and the thickness of the tetrahedral amorphous carbon film with SP3 carbon hybrid bonds is 100-3000 nm.
In some embodiments, the surface functional layer hardness is greater than or equal to 5000HV, and the surface functional layer hardness is greater than the bottom bonding layer hardness.
In some embodiments, a method for preparing a tetrahedral amorphous carbon composite coating comprises the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate 1 to 100-350 ℃;
2) cleaning the surface of the alloy substrate 1 by ion etching;
3) introducing mixed gas of nitrogen and argon, starting a bias power supply and the graphite target material, and depositing a bottom bonding layer CNXA film 2;
4) closing nitrogen, continuously keeping argon gas introduction, keeping turning on a bias voltage power supply and a graphite target, and depositing a surface functional layer high SP (SP) at the temperature of 50-300 DEG C3A tetrahedral amorphous carbon film 3 with carbon hybridized bond content.
In some embodiments, a method for preparing a tetrahedral amorphous carbon composite coating comprises the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate 1 to 100-350 ℃;
2) cleaning the surface of the alloy substrate 1 by ion etching;
3) introducing mixed gas of nitrogen, argon and acetylene, starting a bias power supply and the graphite target material, and depositing a hydrogen-containing CN (carbon nitride) of the bottom bonding layerXA film 2;
4) closing nitrogen and acetylene, continuously keeping argon gas introduction, keeping turning on a bias voltage power supply and a graphite target, and depositing a surface functional layer high SP (SP) at the temperature of 50-300 DEG C3A tetrahedral amorphous carbon film 3 with carbon hybridized bond content.
A process for preparing the tetrahedral amorphous carbon composite coating includes such steps as cleaning the high-speed steel specimen with roughness Ra0.01 by industrial cleaning line, loading it in coating machine, and coating on the surface of specimen facing targetTimber; vacuumizing to be within 5e-4mBar, heating to 300 ℃, and keeping for 1 h; filling a mixed gas of 200sccm argon gas and 1000sccm hydrogen gas into a coating machine cavity, igniting by using a Hall ion source, and applying 50V negative bias on a substrate for ion cleaning for 30 min; introducing mixed gas of 500sccm argon and 500sccm nitrogen into the cavity of the coating machine, applying 200V negative bias on the substrate, igniting the graphite target to generate arc discharge, reacting the generated carbon ions with the nitrogen to a certain extent, and depositing the carbon ions on the high-speed steel substrate under the traction of the negative bias. When CNXStopping nitrogen supply when the thickness of the film bottom binding layer reaches 1000nm, keeping only argon to be introduced to maintain arc discharge, raising the substrate negative bias voltage to 800V to continue depositing Sp3The tetrahedral amorphous carbon film surface functional layer 3 with carbon hybridized bond is as thick as required. The binding force of the high-speed steel test piece is measured by adopting VDI3198 standard and CN-freeXThe test piece bonding force of the bottom bonding layer is HF6 grade, the test piece bonding force of the tetrahedral amorphous carbon composite coating prepared by the method is improved to HF1 grade, the surface functional layer hardness is 5000HV, the surface functional layer hardness is greater than the bottom bonding layer hardness, and the hardness of the prepared tetrahedral amorphous carbon composite coating is improved, so that the antifriction and wear-resistant effects are better.
A preparation method of a tetrahedral amorphous carbon composite coating comprises the steps of cleaning a polished YG8 hard alloy test piece by using an industrial cleaning line, and then putting the cleaned hard alloy test piece into a coating machine, wherein the coating surface faces a target material. The vacuum is pumped to within 5e-4mBar and heated to 100 ℃ and maintained for 1 h. Flushing argon gas of 500sccm into a cavity of a coating machine, igniting by using a Hall ion source, and applying 400V negative bias on a substrate for ion cleaning for 15 min; 500sccm argon gas, 200sccm nitrogen gas and 100sccm mixed gas are introduced into a cavity of a coating machine, 100V negative bias is applied to a substrate, a graphite target is ignited to generate arc discharge, and generated carbon ions, the nitrogen gas and the acetylene react to a certain degree and are deposited on the hard alloy under the traction of the negative bias. When CNXStopping the supply of nitrogen and acetylene when the thickness of the film bottom binding layer reaches 500nm, keeping only argon to be introduced to maintain arc discharge, raising the negative bias voltage of the substrate to 1000V to continue to deposit SP3Tetrahedral amorphous carbon film with carbon hybridized bondTotal thickness of surface functional layer to 1200nm bond strength on cemented carbide test pieces was measured by scratch method (rockwell head diameter 0.2 mm) and the film bond strength of the tetrahedral amorphous carbon composite coating prepared by the above method was L c2 ═ 72.1N, using CN without hydrogenXThe bonding force of the hard alloy test piece of the bottom bonding layer is only L c 2-15.6N, the bonding strength of the prepared tetrahedral amorphous carbon composite coating is obviously improved, the hardness of the surface functional layer is 6000HV, the hardness of the surface functional layer is greater than that of the bottom bonding layer, and the hardness of the prepared tetrahedral amorphous carbon composite coating is improved, so that the antifriction and wear-resistant effects are better.
A tetrahedral amorphous carbon composite coating comprising: a two-layer structure consisting of a bottom bonding layer 2 and a surface functional layer 3, wherein the bottom bonding layer 2 is CN with very high bonding strength with the matrixXFilm, surface functional layer 3 is high SP3A tetrahedral amorphous carbon film with carbon hybridized bond content. The tetrahedral amorphous carbon film composite coating is prepared by a physical vapor deposition process, and preferably adopts an electric arc ion plating and high-power pulse magnetron sputtering process.
A tetrahedral amorphous carbon composite coating adopts CNXThe layer is used as a bottom bonding layer of a tetrahedral amorphous carbon film, the tetrahedral amorphous carbon film is high SP3A tetrahedral amorphous carbon film with carbon hybridized bond content.
The invention provides a tetrahedral amorphous carbon composite coating and a preparation method thereof, and the tetrahedral amorphous carbon composite coating has the following beneficial effects:
1) the invention provides a tetrahedral amorphous carbon composite coating and a preparation method thereof, CNXThe layer has small stress and has better combination effect with iron-based metal, alloy, Cr, Ti and other metals;
2) the invention provides a tetrahedral amorphous carbon composite coating and a preparation method thereof, CNXThe film bottom bonding layer is provided with a large amount of carbon elements, the tetrahedral amorphous carbon film surface functional layer is also composed of the carbon elements, and the interface compatibility between the two is good;
3) the invention provides a tetrahedral amorphous carbon composite coating, a preparation method thereof and a tetrahedral amorphous carbon filmThe surface functional layer is formed by ionizing a graphite target and then rearranging carbon atoms, CNXThe bottom binding layer of the film is generated by the reaction of carbon ions generated by the ionization of the graphite target and nitrogen, the cost of the graphite target and the nitrogen is low, and the tetrahedral amorphous carbon composite coating has extremely high application value and has very high cost advantage.
4) The invention provides a tetrahedral amorphous carbon composite coating and a preparation method thereof, the tetrahedral amorphous carbon composite coating of the preparation method obviously improves the film-substrate bonding strength, and in addition, as the tetrahedral amorphous carbon composite coating has higher hardness than other diamond-like carbon films, the wear-reducing and wear-resisting effects are better and excellent.
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 tetrahedral amorphous carbon composite coating comprising:
bottom bonding layer: is CNXA film;
surface functional layer: is high SP3A tetrahedral amorphous carbon film with carbon-hybridized bond content;
an alloy base material is arranged below the bottom binding layer, and a surface functional layer is arranged above the bottom binding layer.
2. The tetrahedral amorphous carbon composite coating of claim 1, wherein the CNXThe atomic percentage of nitrogen element in the film is 1-50%; x is more than 0 and less than or equal to 1.
3. The tetrahedral amorphous carbon composite coating of claim 1, wherein the CNxThe film is a diamond-like carbon film doped with N element, and the CNXIncluding SP in the film3Carbon hybridized bond.
4. The tetrahedral amorphous of claim 1Carbon composite coating, characterized in that the CNXThe film is doped with any one or more of Si, F, H and S elements through process gas.
5. The tetrahedral amorphous carbon composite coating of claim 1, wherein a metallic bonding layer is provided between the bottom bonding layer and the alloy substrate, the metallic bonding layer being a Ti element metallic bonding layer or a Cr element metallic bonding layer.
6. The tetrahedral amorphous carbon composite coating of claim 1, wherein the CNxThe film is obtained by preparing and depositing a graphite target and nitrogen, and the high SP3The tetrahedral amorphous carbon film with the carbon hybrid bond content is prepared by adopting a physical vapor deposition process through a graphite target and argon, wherein the physical vapor deposition process adopts an electric arc ion plating and high-power pulse magnetron sputtering process.
7. The tetrahedral amorphous carbon composite coating of claim 1, wherein the CNXThe thickness of the film is 50-1000nm, and the SP3The thickness of the tetrahedral amorphous carbon film with carbon hybridization bonds is 100-3000 nm.
8. The tetrahedral amorphous carbon composite coating of claim 1, wherein the surface functional layer hardness is equal to or greater than 5000HV, the surface functional layer hardness being greater than the bottom bonding layer hardness.
9. The preparation method of the tetrahedral amorphous carbon composite coating is characterized by comprising the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate to 100-350 ℃;
2) cleaning the surface of the alloy base material by ion etching;
3) introducing mixed gas of nitrogen and argon, starting a bias power supply and the graphite target material, and depositing a bottom bonding layer CNXA film;
4) shut off the nitrogenContinuously keeping the argon gas introduced, keeping turning on a bias voltage power supply and the graphite target material, and depositing the surface functional layer with high Sp in the environment of 50-300 DEG C3A tetrahedral amorphous carbon film with carbon hybridized bond content.
10. The preparation method of the tetrahedral amorphous carbon composite coating is characterized by comprising the following preparation steps:
1) vacuumizing in an arc ion plating coating machine and heating the alloy substrate to 100-350 ℃;
2) cleaning the surface of the alloy base material by ion etching;
3) introducing mixed gas of nitrogen, argon and acetylene, starting a bias power supply and the graphite target material, and depositing a hydrogen-containing CN (carbon nitride) of the bottom bonding layerxA film;
4) closing nitrogen and acetylene, continuously keeping argon gas introduction, keeping turning on a bias voltage power supply and a graphite target, and depositing a surface functional layer high Sp in an environment with the temperature of 50-300 DEG C3A tetrahedral amorphous carbon film with carbon hybridized bond content.
CN202010390073.1A 2020-05-09 2020-05-09 Tetrahedral amorphous carbon composite coating and preparation method thereof Active CN111500982B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010390073.1A CN111500982B (en) 2020-05-09 2020-05-09 Tetrahedral amorphous carbon composite coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010390073.1A CN111500982B (en) 2020-05-09 2020-05-09 Tetrahedral amorphous carbon composite coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111500982A true CN111500982A (en) 2020-08-07
CN111500982B CN111500982B (en) 2022-04-22

Family

ID=71873290

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010390073.1A Active CN111500982B (en) 2020-05-09 2020-05-09 Tetrahedral amorphous carbon composite coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111500982B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113517189A (en) * 2021-03-30 2021-10-19 长江存储科技有限责任公司 Method for preparing carbon film, carbon film and etching method
CN114086138A (en) * 2021-11-19 2022-02-25 烟台大学 alpha-CNxPreparation method of/Fe nano composite coating
CN114196938A (en) * 2021-12-17 2022-03-18 浙江大学杭州国际科创中心 Double-layer amorphous carbon film and preparation method thereof
CN114990476A (en) * 2022-05-17 2022-09-02 华南理工大学 Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof
CN115312798A (en) * 2022-09-16 2022-11-08 广东省科学院新材料研究所 Metal pole plate surface protective coating, preparation method and application thereof, and metal pole plate
CN115418610A (en) * 2022-09-01 2022-12-02 深圳市商德先进陶瓷股份有限公司 Ceramic cleaver and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132105A (en) * 1990-02-02 1992-07-21 Quantametrics, Inc. Materials with diamond-like properties and method and means for manufacturing them
US20030228496A1 (en) * 2002-05-29 2003-12-11 Hitachi, Inc. Magnetic recording medium and method for manufacturing the same
CN101781748A (en) * 2010-03-31 2010-07-21 西安交通大学 Method for preparing amorphous carbon composite coating on surface of hard alloy material and high-speed steel material
CN104213088A (en) * 2014-08-06 2014-12-17 中国电子科技集团公司第三十八研究所 Method for manufacturing wear-resisting amorphous carbon and nitrogen double-layer thin film on surface of titanium alloy material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132105A (en) * 1990-02-02 1992-07-21 Quantametrics, Inc. Materials with diamond-like properties and method and means for manufacturing them
US20030228496A1 (en) * 2002-05-29 2003-12-11 Hitachi, Inc. Magnetic recording medium and method for manufacturing the same
CN101781748A (en) * 2010-03-31 2010-07-21 西安交通大学 Method for preparing amorphous carbon composite coating on surface of hard alloy material and high-speed steel material
CN104213088A (en) * 2014-08-06 2014-12-17 中国电子科技集团公司第三十八研究所 Method for manufacturing wear-resisting amorphous carbon and nitrogen double-layer thin film on surface of titanium alloy material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘军等: "硬质合金沉积CNx薄膜及其摩擦性能研究", 《化工新型材料》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113517189A (en) * 2021-03-30 2021-10-19 长江存储科技有限责任公司 Method for preparing carbon film, carbon film and etching method
CN114086138A (en) * 2021-11-19 2022-02-25 烟台大学 alpha-CNxPreparation method of/Fe nano composite coating
CN114086138B (en) * 2021-11-19 2024-03-15 烟台大学 alpha-CN x Preparation method of Fe nano composite coating
CN114196938A (en) * 2021-12-17 2022-03-18 浙江大学杭州国际科创中心 Double-layer amorphous carbon film and preparation method thereof
CN114196938B (en) * 2021-12-17 2024-02-20 浙江大学杭州国际科创中心 Double-layer amorphous carbon film and preparation method thereof
CN114990476A (en) * 2022-05-17 2022-09-02 华南理工大学 Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof
CN115418610A (en) * 2022-09-01 2022-12-02 深圳市商德先进陶瓷股份有限公司 Ceramic cleaver and preparation method and application thereof
CN115312798A (en) * 2022-09-16 2022-11-08 广东省科学院新材料研究所 Metal pole plate surface protective coating, preparation method and application thereof, and metal pole plate
CN115312798B (en) * 2022-09-16 2023-12-05 广东省科学院新材料研究所 Metal polar plate surface protective coating, preparation method and application thereof, and metal polar plate

Also Published As

Publication number Publication date
CN111500982B (en) 2022-04-22

Similar Documents

Publication Publication Date Title
CN111500982B (en) Tetrahedral amorphous carbon composite coating and preparation method thereof
CN100506527C (en) Metallic carbide/adamantine (MeC/DLC) nanometer multi-layer film material and preparation method thereof
CN103334106B (en) Surface-hardening treatment method of sealing pairs and friction pairs of titanium and titanium alloy ball valves
CN107034440B (en) A kind of composite diamond carbon film and preparation method thereof
CN101792898B (en) Carbon film for improving abrasion resistance of magnesium alloy and preparation method thereof
CN107022761A (en) Composite thick film and its film plating process based on DLC film
CN108517487B (en) TiAlN/W with high hardness and high wear resistance2N-multilayer coating and method for producing same
CN207313693U (en) Composite thick film based on DLC film
CN101787521B (en) Method for preparing metal sulfide diamond-like carbon composite film
CN107022740A (en) A kind of superhard MULTILAYER COMPOSITE diamond-like coating and preparation method thereof
CN114196914B (en) Carbide high-entropy ceramic material, carbide ceramic layer and preparation method and application thereof
CN107937873A (en) Transition metal boride coating, carbon transition metal boride composite coating, preparation method and application and the cutting element of carbon doping
JP2004169137A (en) Sliding member
CN104294230B (en) High rigidity, multiple elements design diamond-like coating of low stress and preparation method thereof
JP2022525212A (en) Improved coating process
CN108118304A (en) Nano-composite coating and its preparation process
CN106119783A (en) Diamond-like carbon film of functionally gradient and preparation method thereof and goods
CN108265291A (en) A kind of carbon-base coating of soft matrix surface and preparation method thereof
CN109023264B (en) High-hardness TiCN nano composite film and preparation method and mold thereof
JPH10237627A (en) Hard carbon coating-coated member
CN108118305A (en) A kind of tough integrated fullerene carbon nitrogen multi-layer compound film and preparation method thereof
CN112853281A (en) Carbon-based multilayer film and preparation method and application thereof
JPH10226874A (en) Hard carbon coating and coating member and coated member therewith
JP2000177046A (en) Member coated with diamondlike carbon film
CN110343998B (en) Printed circuit board drill point ta-C coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant