CN109518184B - Hf-BHfN-BHfNC composite coating cutter and preparation method thereof - Google Patents

Hf-BHfN-BHfNC composite coating cutter and preparation method thereof Download PDF

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CN109518184B
CN109518184B CN201811406259.0A CN201811406259A CN109518184B CN 109518184 B CN109518184 B CN 109518184B CN 201811406259 A CN201811406259 A CN 201811406259A CN 109518184 B CN109518184 B CN 109518184B
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coating
bhfn
bhfnc
cutter
transition layer
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CN109518184A (en
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吴泽
赵国龙
邢佑强
黄鹏
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Southeast University
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Southeast University
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C14/0635—Carbides
    • 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
    • C23C14/0664—Carbonitrides
    • 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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

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

Abstract

The invention belongs to the technical field of cutter coating materials, and relates to a Hf-BHfN-BHfNC composite coating cutter and a preparation method thereof. The base material of the cutter is a high-speed steel material, and the coating comprises a Hf transition layer, a BHfN hard coating and a BHfNC hard coating from inside to outside in sequence. The Hf transition layer of the coated cutter is prepared by electroplating and heat treatment processes, and the BHfN layer and the BHfNC layer are both prepared by a reactive magnetron sputtering method. The transition layer material of the coated cutter and the base material of the cutter are deeply diffused, the coating and the base have higher bonding strength, and the surface coating has high hardness and good wear resistance. The cutter can be widely applied to cutting processing of low-hardness metal materials, and the service life and the cutting processing efficiency of the cutter are improved.

Description

Hf-BHfN-BHfNC composite coating cutter and preparation method thereof
Technical Field
The invention relates to a Hf-BHfN-BHfNC composite coating cutter and a preparation method thereof, belonging to the technical field of cutter coating materials.
Background
The mechanical manufacturing industry provides technical equipment for the whole national economy, is a material foundation for national economy and social development and national defense construction, and the development level of the mechanical manufacturing industry is an important mark of national comprehensive strength. The cutting technology is the most widely applied basic technology in the machine manufacturing industry, and the progress of the cutting tool technology is the key for the rapid development of the cutting technology. In recent years, in order to meet new requirements for cutting tools such as dry cutting and high-speed cutting, the metal cutting tool industry is continuously trying to develop new wear-resistant tool materials, tool coatings and develop optimized designs of tool geometric structures, and the methods all solve the bottleneck problem of limiting the development of cutting technology to a certain extent. Among these methods, the coating is most widely applicable, but the bonding problem between the coating and the base material becomes a large factor that restricts the performance, and particularly the bonding performance of the coating to the transition layer of the bonding portion of the tool base is important. For this reason, the development of new high bond strength coated tools will be of great significance to facilitate the expansion of the range of applications of coated tools and the advancement of cutting machining technology.
Chinese patent "application number: 201710532821.3 reports an AlNbCN multi-component gradient composite coating cutter and a preparation method thereof, the invention adopts a composite method of medium-frequency magnetron sputtering and multi-arc plating to sequentially deposit a Ti transition layer, an AlNbC transition layer and an AlNbCN coating with gradually changed nitrogen content gradient on the surface of a cutter substrate, and the cutter has higher hardness and strength. Chinese patent "application number: 201710532803.5 reports a SiNbC/SiNbCN laminated composite coating cutter and a preparation process thereof, the two composite coatings are alternately deposited on the surface of a cutter substrate by non-equilibrium magnetron sputtering and arc ion plating methods, and the cutter has good physical and mechanical properties and can be applied to finish machining and semi-finish machining of various metal materials.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects of the prior art and provides a Hf-BHfN-BHfNC composite coating cutter and a preparation method thereof, which further improve the bonding strength of a coating film substrate and the physical and mechanical properties of a coating film.
The technical scheme is as follows: according to the Hf-BHfN-BHfNC composite coating cutter, the base material of the cutter is a high-speed steel material, and the cutter coating sequentially comprises an Hf transition layer, a BHfN hard coating and a BHfNC hard coating from inside to outside.
The preparation method of the Hf-BHfN-BHfNC composite coating cutter comprises the following steps: first using HfCl4Electroplating and depositing a Hf transition layer on the surface of a high-speed steel cutter base body by using an electrolyte, wherein the concentration of the electrolyte is 5-10 wt.%, the anode is a metal hafnium material, the thickness of the electroplated and deposited transition layer is 0.2-0.5 mu m, and the cutter after the electroplated and deposited transition layer is placed into a vacuum heating furnace to be heated to 300-500 ℃ for heat preservation, so that the diffusion of the hafnium element and the cutter base body material is promoted, and the transition layer with high bonding strength is formed; depositing a BHfN coating on the surface of the transition layer by adopting a magnetron sputtering method, selecting high-purity elemental boron and elemental hafnium as a radio frequency target material, introducing mixed gas of nitrogen and argon, wherein the mass fraction ratio of the nitrogen to the argon is 1:5, the deposition pressure is 0.6-1.0Pa, and the thickness of the deposited BHfN coating reaches 0.5-0.8 mu m; a magnetron sputtering method is adopted to deposit a BHfNC coating on the surface of the BHfN layer, boron carbide and simple substance hafnium are selected as radio frequency targets, mixed gas of nitrogen and argon is introduced, the deposition temperature is 350-450 ℃, and the thickness of the deposited BHfNC coating reaches 0.5-1.0 mu m.
Has the advantages that: the invention deposits a novel Hf-BHfN-BHfNC composite coating on the surface of the high-speed steel cutter by combining an electroplating and magnetron sputtering integrated process method. Compared with the conventional titanium nitride-based coating, the novel composite coating has higher hardness, and the metal hafnium as a transition layer is more compact than the conventional titanium transition layer; compared with the existing single PVD coating method, the transition layer preparation process combining electroplating and heat treatment can effectively promote the diffusion of the elements of the transition layer and the base material, and obviously enhance the bonding strength of the coating and the base. The Hf-BHfN-BHfNC composite coating cutter can be widely applied to cutting machining of low-hardness metal materials, and the service life and the cutting machining efficiency of the cutter are improved.
Drawings
FIG. 1 is a schematic view of the coating structure of the Hf-BHfN-BHfNC composite coating cutter of the invention, wherein: and the Hf transition layer, the BHfN layer and the BHfNC layer are arranged along the outside of the cutter base body in sequence.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example (b):
a Hf-BHfN-BHfNC composite coating turning tool is characterized in that a tool base material is a high-speed steel material, and a tool coating comprises a Hf transition layer, a BHfN hard coating and a BHfNC hard coating from inside to outside in sequence.
The preparation method of the Hf-BHfN-BHfNC composite coating turning tool comprises the following steps:
(1) pretreatment: and mechanically polishing the cutting working area of the high-speed steel turning tool, putting the high-speed steel turning tool into absolute ethyl alcohol, ultrasonically cleaning for 20min, and drying in vacuum.
(2) Using HfCl4Electroplating and depositing a Hf transition layer on the surface of the high-speed steel cutter substrate cleaned and dried by electrolyte, wherein the concentration of the electrolyte is 10 wt.%, the anode is a metal hafnium material, the thickness of the electroplating and depositing transition layer is 0.4 mu m, and the cutter after the electroplating and depositing transition layer is placed into a vacuum heating furnace to be heated to 500 ℃ and is kept warm for 3hThe diffusion of the hafnium element and the high-speed steel matrix material is promoted, and the Hf transition layer with high bonding strength is formed.
(3) A BHfN coating is deposited on the surface of the transition layer by adopting a magnetron sputtering method, high-purity elemental boron and elemental hafnium are selected as radio frequency targets, mixed gas of nitrogen and argon is introduced, the mass fraction ratio of the nitrogen to the argon is 1:5, the deposition pressure is 0.8Pa, and the thickness of the deposited BHfN coating reaches 0.6 mu m.
(4) And (3) depositing a BHfNC coating on the surface of the BHfN layer by adopting a magnetron sputtering method, selecting boron carbide and simple substance hafnium as radio frequency targets, introducing mixed gas of nitrogen and argon, and depositing the BHfNC coating at the deposition temperature of 400 ℃ until the thickness of the BHfNC coating reaches 0.8 mu m to finish the preparation of the coated cutter.

Claims (4)

1. The Hf-BHfN-BHfNC composite coating cutter is characterized in that: the base material of the cutter is a high-speed steel material, and the coating comprises a Hf transition layer, a BHfN hard coating and a BHfNC hard coating from inside to outside in sequence; the composite coating cutter is prepared by the following method: depositing Hf element on the surface of a high-speed steel cutter substrate by adopting an electroplating method, and promoting the diffusion of the Hf element and the substrate material by heat treatment to form a transition layer with high bonding strength; and respectively and sequentially depositing a BHfN coating and a BHfNC coating on the surface of the transition layer by adopting a magnetron sputtering method.
2. The Hf-BHfN-BHfNC composite coated tool of claim 1, wherein: the electrolyte used for the electrolytic deposition of the transition layer is HfCl4The concentration of the electrolyte is 5-10 wt.%, the anode is a metal hafnium material, and the thickness of the electroplating deposition transition layer is 0.2-0.5 μm; and (3) performing heat preservation on the transition layer in a vacuum heating furnace, wherein the heating temperature is kept at 300-500 ℃.
3. The Hf-BHfN-BHfNC composite coated tool of claim 1, wherein: the preparation method of the BHfN coating comprises the steps of selecting high-purity elemental boron and elemental hafnium as radio frequency targets, introducing mixed gas of nitrogen and argon, wherein the mass fraction ratio of the nitrogen to the argon is 1:5, the deposition pressure is 0.6-1.0Pa, and the thickness of the deposited BHfN coating reaches 0.5-0.8 mu m.
4. The Hf-BHfN-BHfNC composite coated tool of claim 1, wherein: the preparation method of the BHfNC coating adopts boron carbide and simple substance hafnium as radio frequency targets, mixed gas of nitrogen and argon is introduced, the deposition temperature is 350-450 ℃, and the thickness of the deposited BHfNC coating reaches 0.5-1.0 mu m.
CN201811406259.0A 2018-11-23 2018-11-23 Hf-BHfN-BHfNC composite coating cutter and preparation method thereof Active CN109518184B (en)

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CN111254384A (en) * 2019-10-10 2020-06-09 东南大学 Hf-AlHfSiN-AlHfNdN composite coating cutter
CN111411335B (en) * 2020-03-02 2022-06-28 杭州电子科技大学 Ag @ SiO distributed in large area2Preparation method and application of nanoparticles

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US5948541A (en) * 1996-04-04 1999-09-07 Kennametal Inc. Boron and nitrogen containing coating and method for making
US20070256937A1 (en) * 2006-05-04 2007-11-08 International Business Machines Corporation Apparatus and method for electrochemical processing of thin films on resistive substrates
US20130052475A1 (en) * 2011-08-23 2013-02-28 Korea Institute Of Science And Technology Method of fabricating porous film structure using dry processes and porous film structures fabricated by the same
CN107177828B (en) * 2017-07-03 2019-08-06 济宁学院 SiZrCN gradient composite coating cutter and preparation method thereof

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