WO2017136970A1 - TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法 - Google Patents

TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法 Download PDF

Info

Publication number
WO2017136970A1
WO2017136970A1 PCT/CN2016/075350 CN2016075350W WO2017136970A1 WO 2017136970 A1 WO2017136970 A1 WO 2017136970A1 CN 2016075350 W CN2016075350 W CN 2016075350W WO 2017136970 A1 WO2017136970 A1 WO 2017136970A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
composite coating
tialsizrn
wear
substrate
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.)
Ceased
Application number
PCT/CN2016/075350
Other languages
English (en)
French (fr)
Inventor
伍尚华
陈健
邓欣
刘伟
何福坡
陈少华
刘汝德
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Publication of WO2017136970A1 publication Critical patent/WO2017136970A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/027—Graded interfaces
    • 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
    • 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
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating

Definitions

  • the invention relates to the technical field of cemented carbide cutters, in particular to a TiAlSiZrN-based composite coating, a gradient ultra-fine cemented carbide cutter having the composite coating and a preparation method thereof.
  • This application is based on the Chinese invention patent application with the application number 2016100835077 and the application date being February 11, 2016.
  • coated carbide tools is an important milestone in the history of tool development. It is formed by coating a thin layer of refractory metal or non-metal compound with good wear resistance by a vapor deposition method on a cemented carbide substrate having good strength and toughness.
  • the coating reduces the diffusion and chemical reaction between the tool and the workpiece, thus reducing crater wear.
  • the coating has high hardness and heat resistance and reduces the coefficient of friction between the tool and the workpiece. Therefore, the coated tool can significantly improve the service life than the uncoated tool. Generally, the life of the coated tool can be compared with that of the uncoated tool. 2-5 times higher.
  • Carbide tools are subjected to great mechanical and thermal loads during processing, which are prone to wear and tear, which affects their service life.
  • Surface modification of tool materials improves surface properties and improves the service life of tool materials.
  • Applying a thin layer of high-hardness and wear-resistant materials such as TiN, TiN, TiCN or Al 2 O 3 on the surface of the cemented carbide can improve the wear resistance of the tool while maintaining good toughness of the substrate, which can significantly improve the working performance of the tool material and Service life.
  • the coating is basically a hard and brittle material, and the coefficient of thermal expansion of the cemented carbide substrate is different. There is a stress concentration at the interface between the coating and the substrate, and usually the crack is easily generated on the surface of the coating and diffused into the interior of the alloy. The material failed.
  • TiN is the first hard coating material that is widely used. TiN coating has superior performance and the process is in line with the "green manufacturing" concept, but TiN has limited temperature resistance. When the temperature exceeds 500 °C, the oxidation resistance is deteriorated, which still limits its application fields. With the advancement of technology, people have higher and higher requirements for the comprehensive performance of coatings. For products with different service conditions, the tool base with specific surface properties should be adapted to the specific composite coating to increase the coating. The bonding force between the layer and the substrate and the abrasion resistance of the coating.
  • One of the objects of the present invention is to provide a TiAlSiZrN-based composite coating and a preparation method thereof, which avoids the deficiencies of the prior art, and the TiAlSiZrN-based composite coating has good bonding property with the tool base, and the coating of the composite coating is attached. Good strength, high density, high temperature resistance, corrosion resistance, wear resistance, and good lubricity of the composite coating. .
  • Another object of the present invention is to provide a gradient ultrafine with a TiAlSiZrN-based composite coating Carbide tools with good wear and temperature resistance.
  • TiAlSiZrN-based composite coating comprising a TiN layer for depositing as a transition layer on a tool surface, a TiN/TiSiN layer deposited as a support layer on the transition layer, a TiSiN layer deposited as a wear layer on the support layer, and A TiAlSiZrN layer deposited as a wear-reducing layer on the wear-resistant layer, the support layer being alternately composed of a TiN layer and a TiSiN layer.
  • the thickness of the transition layer is 500-2000 nm; the thickness of the support layer is 500-4000 nm; the thickness of the wear layer is 500-4000 nm; the thickness of the wear-reducing layer is 500-4000 nm;
  • the thickness of the single-layer TiSiN layer is 9-15 nm
  • the thickness of the single-layer TiSiN layer is 8-16 nm
  • the sum of the thicknesses of the adjacent two TiSiN layers and the TiN layer is 17-31 nm.
  • a method for preparing a TiAlSiZrN-based composite coating wherein a TiN layer as a transition layer, a TiN/TiSiN layer deposited as a support layer on a transition layer, and a wear layer are deposited on the support layer by an arc ion plating method.
  • the transition layer is deposited under a nitrogen atmosphere at a pressure of 0.1-0.5 Pa and a voltage of 100 V-250 V;
  • the support layer is deposited under a nitrogen atmosphere at a pressure of 0.5 to 2.3 Pa, a voltage of 150 V to 250 V;
  • the wear layer is deposited under a nitrogen atmosphere at a pressure of 0.1-lPa and a voltage of 150V-250V;
  • the anti-friction layer is deposited under a nitrogen atmosphere at a gas pressure of 0.1-0.5 Pa and a voltage of 150 V-250 V.
  • the preparation method of the above TiAlSiZrN-based composite coating layer is as follows:
  • the arc ion plating equipment is evacuated to 1.52 ⁇ 10 -2 Pa or less, and then the furnace body is heated to 450-550 ° C, and the arc ion plating equipment is kept evacuated and the internal air pressure is not more than 10 -3 Pa;
  • the preparation method of the above TiAlSiZrN-based composite coating layer is specifically prepared as follows.
  • the arc ion plating equipment is evacuated to 1.52 ⁇ 10 -2 Pa or less, and then the furnace body is heated to 500 ° C, and the arc ion plating equipment is kept evacuated and the internal air pressure is not more than 10 -3 Pa;
  • Ar+ obtains high particle energy under the substrate bias of 1250 V to bombard and invade the candle matrix, and remove impurities on the surface of the substrate;
  • the tool substrate is provided with a normal tissue layer, a cobalt-rich transition layer and a cobalt-poor cubic phase layer, and the normal tissue layer, the cobalt-rich transition layer and the cobalt-poor cubic phase layer are arranged in order from the inside to the outside;
  • the TiAlSiZrN-based composite coating is composed of a TiN layer as a transition layer, a TiN/TiSiN layer deposited as a support layer on the transition layer, a TiSiN layer deposited as a wear layer on the support layer, and deposited on the wear layer. a layer of a TiAlSiZrN layer of the grinding layer, the support layer being alternately composed of a TiN layer and a TiSiN layer;
  • the transition layer is deposited on the surface of the cobalt-depleted cubic phase layer.
  • the content of cobalt in the tool base is 5-15 wt.%
  • the normal tissue layer is an ultrafine cemented carbide, and the WC grain size is 1-1000 nm;
  • the thickness of the normal tissue layer is greater than 2 mm, the thickness of the cobalt-rich transition layer is 20-100 um; the thickness of the cobalt-poor rich cubic phase layer is 20-50 um;
  • the thickness of the transition layer is 500-2000 nm; the thickness of the support layer is 500-4000 nm; the thickness of the wear layer is 500-4000 nm; the thickness of the wear-reducing layer is 500-4000 nm;
  • the thickness of the single-layer TiSiN layer is 9-15 nm
  • the thickness of the single-layer TiSiN layer is 8-16 nm
  • the sum of the thicknesses of the adjacent two TiSiN layers and the TiN layer is 17-31 nm.
  • the content of cobalt in the tool base is 8-12 wt.%
  • the normal tissue layer is an ultrafine cemented carbide with a WC grain size of 1-400 nm.
  • the gradient ultra-fine cemented carbide tool having a TiAlSiZrN-based composite coating layer is deposited on the cobalt-depleted cubic phase layer by an arc ion plating method, and the support layer is deposited by an arc ion plating method.
  • a wear layer is deposited on the support layer by an arc ion plating method, and the wear reduction layer is deposited on the wear layer by an arc ion plating method;
  • the transition layer is deposited under a nitrogen atmosphere at a pressure of 0.1-0.5 Pa and a voltage of 100 V-250 V;
  • the support layer is deposited under a nitrogen atmosphere at a pressure of 0.5 to 2.3 Pa, a voltage of 150 V to 250 V;
  • the wear layer is deposited under a nitrogen atmosphere at a pressure of 0.1-lPa and a voltage of 150V-250V;
  • the anti-friction layer is deposited under a nitrogen atmosphere at a gas pressure of 0.1-0.5 Pa and a voltage of 150 V-250 V.
  • the preparation process of the TiAlSiZrN-based composite coating having the TiAlSiZrN-based composite coating and the TiAlSiZrN-based composite coating is as follows.
  • the arc ion plating equipment is evacuated to 1.4 ⁇ 10 -2 Pa or less, and then the furnace body is heated to 450-550 ° C, and the arc ion plating equipment is kept evacuated and the internal air pressure is not more than 10 -3 Pa;
  • the TiAlSiZrN-based composite coating of the invention has good bonding property with the tool base, the adhesion between the coatings of the composite coating is good, the density is high, the high temperature resistance, the corrosion resistance and the wear resistance are good, and the composite coating layer Good lubrication performance.
  • the gradient ultra-fine cemented carbide tool with the TiAlSiZrN-based composite coating has good wear resistance and temperature resistance.
  • Fig. 1 is a schematic view showing the interlayer structure of a TiAlSiZrN-based composite coating layer of the present invention.
  • FIG. 2 is a schematic view showing the interlayer structure of a gradient ultrafine cemented carbide tool having a TiAlSiZrN-based composite coating layer according to the present invention.
  • FIG 3 is a schematic view of a gradient ultra-fine cemented carbide tool having a TiAlSiZrN-based composite coating of the present invention.
  • a TiAlSiZrN-based composite coating includes a surface for deposition on a tool surface A TiN layer of a transition layer, a TiN/TiSiN layer deposited as a support layer on the transition layer, a TiSiN layer deposited as a wear layer on the support layer, and a TiAlSiZrN layer deposited as a wear-reducing layer on the wear layer.
  • the thickness of the transition layer is 500-2000 nm; the thickness of the support layer is 500-4000 nm; the thickness of the wear-resistant layer is 500-4000 nm; and the thickness of the wear-reducing layer is 500-4000 nm.
  • the support layer is composed of a TiN layer and a TiSiN layer alternately, wherein the thickness of the single TiSiN layer is 9-15 nm, the thickness of the single TiSiN layer is 8-16 nm, and the sum of the thicknesses of the adjacent two TiSiN layers and the TiN layer. It is 17-31 nm.
  • the TiAlSiZrN-based composite coating is sequentially deposited by a plasma ion plating method as a TiN layer as a transition layer, a TiN/TiSiN layer deposited as a support layer on the transition layer, a TiSiN layer deposited as a wear layer on the support layer, and deposited on the TiSiN layer.
  • a TiAlSiZrN layer as a wear-reducing layer on the wear-resistant layer.
  • the transition layer is deposited under a nitrogen atmosphere at a pressure of 0.1-0.5 Pa and a voltage of 100 V-250 V;
  • the support layer is deposited under a nitrogen atmosphere at a pressure of 0.5-2.3 Pa, a voltage of 150 V-250 V;
  • the wear layer is deposited under a nitrogen atmosphere at a pressure of 0.1-lPa and a voltage of 150V-250V;
  • the anti-friction layer is deposited under a nitrogen atmosphere at a pressure of 0.1-0.5 Pa and a voltage of 150 V-250 V.
  • the Ti ions are evaporated from the Ti target at a high temperature and moved to the surface of the cemented carbide blade under high bias.
  • the surface of the cemented carbide insert is subjected to a negative high pressure of 1000-1200 V.
  • the high pressure accelerates the ionized Ti ions.
  • the accelerated Ti ions will hit the surface of the cemented carbide blade at high speed, and the impact process will generate high temperature.
  • Ti ions will form a metallurgical bonding layer with the cemented carbide blade matrix. Generally, the diffusion depth reaches 5-10nm.
  • the bombardment effect of Ti ions can be Forming a metallurgical bonding layer, and secondly, The deposition of a pure Ti layer on the surface of the cemented carbide insert, due to the simultaneous bombardment and deposition process, the Ti coating formed will be very dense, inhibiting the growth of the columnar Ti coarse grains. Nitrogen is then introduced into the Ti to form a TiN transition layer. The thickness of the transition layer is generally from 100 to 300 nm. On the basis of the TiN coating, the TiSi target is gradually opened, and TiSi reacts with nitrogen to form a TiSiN coating. When the alloy knife moves to the front of the Ti target, a TiN coating is formed, and when moved to the front of the TiSi target, a TiSiN coating is formed. The continuous rotation of the alloy knife will form a TiN/TiSiN nanocomposite coating as a support layer.
  • the combination of the two not only makes the TiSiN and the underlying TiN have a good bonding force, but also greatly reduces the internal stress of the coating while maintaining the hardness.
  • the thickness of the support layer is generally from 500 to 1500 nm. When the support layer is deposited, the coating has a certain thickness and hardness. In order to improve its temperature resistance, the Ti target is turned off, and a pure TiSiN coating with good temperature resistance is deposited. The size of the TiN nanocrystal in the TiSiN coating. It has a great influence on the hardness and temperature resistance of the coating. For this reason, the size of the TiN nanocrystals must be controlled, generally controlled at 5-20 nm.
  • the composite coating not only has good wear resistance, but also has good corrosion resistance due to the multilayer structure. Compared with the conventional single-layer TiN, due to the addition of TiSiN coating material, the coating not only has good wear resistance, but also its lubricating performance is greatly increased. In addition, the TiN/TiSiN layer gradient design provides a better support for the high hardness wear layer, and the surface TiAlSiZrN composite wear layer has better wear resistance.
  • TiSiN nanocrystalline composite coating is mainly to provide a compositional gradation between the TiN layer and the TiSiN layer and between the TiSiN layer and the TiAlSiZrN layer, thereby achieving a good stress reduction effect.
  • TiSiN coating TiAlSiZrN layer is deposited to form TiSiN/TiAlSiZrN interlayer structure layer.
  • TiAlSiZrN layer not only has high hardness, but also has certain anti-wear performance, lowering the friction coefficient of composite coating, when processing various materials. Provide better lubrication performance and improve processing results. For this reason, the coating not only has an advanced structural design, but also the combination of a plurality of materials makes the coating have good adaptability.
  • the composite coating of the invention is used for depositing on the surface of the cemented carbide tool base.
  • the bond with the tool base is good, and the prepared tool has good wear resistance and temperature resistance, and the Improve the processing performance of cemented carbide tools.
  • Ar+ obtains high particle energy under the substrate bias of 1250 V to bombard and invade the candle matrix, and remove impurities on the surface of the substrate;
  • the TiAlSiZrN-based composite coating prepared in this embodiment has good bonding property with the tool base, the adhesion between the coating layers of the composite coating is good, the density is high, the high temperature resistance, the corrosion resistance and the wear resistance are good, and The composite coating has good lubricating properties.
  • the gradient ultra-fine cemented carbide tool with the TiAlSiZrN-based composite coating has good wear resistance and temperature resistance.
  • a gradient ultra-fine cemented carbide tool having a TiAlSiZrN-based composite coating consisting of a tool base and a TiAlSiZrN-based composite coating disposed on the tool body, as shown in FIGS. 2 and 3.
  • the tool base is provided with a normal tissue layer, a cobalt-rich transition layer and a cobalt-depleted cubic phase layer, and the normal tissue layer, the cobalt-rich transition layer and the cobalt-depleted cubic phase layer are arranged in order from the inside to the outside.
  • the content of cobalt in the tool base is 5-15 wt.%, preferably the content of cobalt is 8-12 wt.%.
  • the normal tissue layer is an ultrafine cemented carbide having a WC grain size of 1-1000 nm, preferably a WC grain size of 1-500 nm.
  • the cobalt-depleted cubic phase layer is rich in cubic phase nitrides or carbonitrides, and the cubic phase nitrides and carbonitrides in the cemented carbide have a higher hardness than the densely packed hexagonal phase WC. Therefore, the cobalt-poor rich cube
  • the surface layer of the phase has a higher hardness.
  • the binder phase rich in the cobalt-rich transition layer when the crack formed in the coating diffuses into the region, can absorb the energy of the crack diffusion due to its good toughness, and therefore can effectively prevent the crack from diffusing into the alloy. Moreover, it can better absorb the impact energy of the cutting tool, and thus has high impact toughness characteristics, thereby contributing to the improvement of the service life of the tool material.
  • the core is a rigid tissue region, that is, a normal tissue layer, and the WC crystal grain distribution is uniform and fine, and the average WC grain size is ⁇ 500 nm, which has excellent mechanical properties of the ultrafine cemented carbide.
  • the TiAlSiZrN-based composite coating consists of a TiN layer as a transition layer, a TiN/TiSiN layer deposited as a support layer on the transition layer, a TiSiN layer deposited as a wear layer on the support layer, and deposited on the wear layer as a wear-reducing layer.
  • the TiAlSiZrN layer is formed; the transition layer is deposited on the surface of the cobalt-depleted cubic phase layer.
  • the thickness of the normal tissue layer is greater than 2 mm
  • the thickness of the cobalt-rich transition layer is 20-100 um
  • the thickness of the cobalt-depleted cubic phase layer is 20-50 um.
  • the thickness of the transition layer is 500-2000 nm; the thickness of the support layer is 500-4000 nm; the thickness of the wear-resistant layer is 500-4000 nm; and the thickness of the wear-reducing layer is 500-4000 nm.
  • the support layer is composed of a TiN layer and a TiSiN layer alternately, wherein the thickness of the single TiSiN layer is 9-15 nm, the thickness of the single TiSiN layer is 8-16 nm, and the sum of the thicknesses of the adjacent two TiSiN layers and the TiN layer is 17-31 nm.
  • the gradient ultra-fine cemented carbide tool with TiAlSiZrN-based composite coating of the invention adopts nano-multilayer composite coating on the surface of the cobalt-rich and rich cubic phase gradient ultrafine cemented carbide tool base, which can effectively control the matrix gradient and
  • the structure and composition of the coating, the TiAlSiZrN-based composite coating has a good bonding force with the substrate, and the formed tool has good wear resistance and temperature resistance.
  • the tool base of the invention consists of three layers from the inside to the outside, which are a normal tissue layer, a cobalt-rich transition layer, and a cobalt-poor rich cubic phase layer.
  • the cobalt-depleted cubic phase layer is rich in cubic phase nitrides or carbonitrides, and the cubic phase nitrides and carbonitrides in the cemented carbide have a higher hardness than the densely packed hexagonal phase WC.
  • the surface layer of the cobalt-depleted cubic phase has higher hardness; the binder phase rich in the cobalt-rich transition layer can absorb crack propagation due to good toughness when the crack formed in the coating diffuses into the region.
  • the energy of the time therefore, can effectively prevent the crack from diffusing into the interior of the alloy, and can better absorb the impact energy during cutting of the tool, thereby having high impact toughness characteristics, thereby contributing to improving the service life of the tool material;
  • the WC grain distribution is uniform and fine (average WC grain size ⁇ 500 nm), and the tool substrate has excellent mechanical properties.
  • the invention fully utilizes nanocrystalline amorphous composite, nano multilayer composite, gradient composite and multilayer structure coating technology to form a structure and composition gradient, and the coating has good adhesion with the substrate and the coating.
  • the invention adopts the multi-layer structure technology to suppress the growth of the columnar crystals, improve the density of the coating layer, and enhance the corrosion resistance of the composite coating layer, and the wear resistance is also greatly improved.
  • the prepared tool has good corrosion resistance and wear resistance.
  • the invention constructs a novel wear-resistant and self-lubricating coating by setting a TiSiN layer with good temperature resistance and a TiAlSiZrN layer with low friction coefficient, and breaks the shortcoming of poor lubrication performance of the existing tool coating, and the prepared tool has good performance. Lubrication performance.
  • the gradient ultra-fine cemented carbide tool with the TiAlSiZrN-based composite coating of the invention has a greatly improved cutting performance compared to the conventional cemented carbide tool.
  • a gradient ultra-fine cemented carbide tool with a TiAlSiZrN-based composite coating comprises the preparation of a tool base and deposition of a TiAlSiZrN-based composite coating on the surface of the tool substrate.
  • the transition layer is a TiN layer; the transition layer is used to improve the bonding force with the tool base and reduce the internal stress;
  • the wear layer is a TiSiN layer; the wear layer is used for improving hardness, strength and oxidation resistance;
  • the antifriction layer is laminated on the wear layer obtained above, and the antifriction layer is a TiAlSiZrN layer; the antifriction layer can improve the oxidation resistance and reduce the friction coefficient.
  • the gradient ultra-fine cemented carbide tool with TiAlSiZrN-based composite coating prepared in this embodiment has good bonding property with the tool base, and the alloy tool has high temperature resistance, corrosion resistance and wear resistance, and is compounded.
  • the coating has good lubricating properties.
  • a gradient ultra-fine cemented carbide tool with a TiAlSiZrN-based composite coating comprises the preparation of a tool base and deposition of a TiAlSiZrN-based composite coating on the surface of the tool substrate.
  • the tool base is sintered from the following mass percent components: 5-15% TiC, 2-5% TaC, 10-15% alloy binder phase, and the balance is WC.
  • the alloy binder phase consists of the following mass percentages of powder: 0.5-5.5% Cr, 0.5-5.5% Mo, 0.5-5.5% B, 0.5-5.5% Al, 0.5-5.5% V, 0.5- 5.5% Y, 0.5-5.5% Si, the balance is Co, and the sum of the masses of Cr, Mo, B, Al, V, Y and Si in the alloy binder phase is 7-20 of the quality of the alloy binder phase. %.
  • the preparation method of the tool base comprises the following steps:
  • alloy binder phase Eight kinds of powders of Cr, Mo, B, Al, V, Y, Si and Co are weighed according to the mass percentage, and eight kinds of powders are uniformly mixed to obtain an alloy binder phase. Preferably, eight powders are placed in a ball mill, ball milled with a cemented carbide ball for 72 hours, and ball milled for 10 minutes after each ball mill for 1 hour to obtain an alloy binder phase.
  • the blank can be first press-molded by a molding machine to obtain a green body; and the green body is further pressed by a cold isostatic press to obtain a green body.
  • the blank is placed in a sintering furnace, heated to 1200-1250 ° C at a rate of 5-8 ° C / min, maintained for 18-22 min, and maintained at a vacuum below 10 -3 Pa; then into the sintering furnace Fill with nitrogen and raise the temperature to 1420-1450 ° C at 1-3 ° C / min, keep the pressure for 55-65 min and maintain the pressure above 0.2 MPa; then cool down to 1000-1200 ° C at 2-6 ° C / min, The temperature is maintained for 110-130 min, and the pressure of 0.2 MPa or more is maintained; then the green body is cooled with the furnace and maintained at a pressure of 0.2 MPa or more to obtain a surface hardened gradient cemented carbide.
  • a pre-sintering step is performed in which the green body is placed in a sintering furnace and sintered at 1400 ° C for 10 min under an inert gas atmosphere; the green body is refined with the furnace to refine the shape of the green body.
  • the cemented carbide substrate prepared by the method has excellent mechanical properties and improves the red hardness of the cemented carbide.
  • the grain in the cemented carbide matrix is fine, the surface layer of the cemented carbide is rich in cubic phase and lean in the binder phase, and there is also an excessive layer of alloyed binder phase under the surface layer, so that the cemented carbide has excellent hardness and resistance. Grindability and toughness.
  • the alloy substrate After the alloy substrate is prepared, it is chemically cleaned, and then a TiAlSiZrN-based composite coating is deposited on the surface thereof.
  • the transition layer is deposited on the cobalt-depleted cubic phase layer by an arc ion plating method
  • the support layer is deposited on the transition layer by an arc ion plating method
  • the wear layer is deposited on the support layer by an arc ion plating method.
  • the wear-reducing layer is deposited on the wear layer by an arc ion plating method.
  • the transition layer is sinked under a nitrogen atmosphere at a pressure of O.1-0.5Pa and a voltage of 100V-250V.
  • the support layer is deposited under a nitrogen atmosphere at a pressure of 0.5-2.3 Pa, a voltage of 150 V-250 V;
  • the wear layer is deposited under a nitrogen atmosphere at a pressure of 0.1-lPa and a voltage of 150V-250V;
  • the anti-friction layer is deposited under a nitrogen atmosphere at a pressure of 0.1-0.5 Pa and a voltage of 150 V-250 V.
  • the deposition process of the TiAlSiZrN-based composite coating is as follows,
  • the gradient ultra-fine cemented carbide tool with TiAlSiZrN-based composite coating prepared by the invention adopts nano-multilayer composite coating on the surface of the cobalt-rich and rich cubic phase gradient ultrafine cemented carbide tool base, which can be effectively controlled
  • the matrix gradient and the structure and composition of the coating, the TiAlSiZrN-based composite coating has a good bonding force with the substrate, and the formed tool has good wear resistance and temperature resistance.
  • the tool base tool base of the invention has excellent mechanical properties, and has good adhesion between the composite coating and the substrate and the coating, and the tool has good corrosion resistance, friction resistance and self-lubricating performance.
  • the gradient ultra-fine cemented carbide tool having the TiAlSiZrN-based composite coating prepared by the invention has greatly improved the cutting performance compared with the conventional cemented carbide tool.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

一种TiAlSiZrN基复合涂层、具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具及其制备方法。TiAlSiZrN基复合涂层由TiN层、TiN/TiSiN层、TiSiN层和TiAlSiZrN层构成。合金刀具由刀具基体和TiAlSiZrN基复合涂层构成。刀具基体设置有正常组织层、富钴过渡层和贫钴富立方相层。复合涂层通过电弧离子镀设备沉积而成。TiAlSiZrN基复合涂层，其与刀具基体结合性良好，复合涂层的涂层之间附着力良好，致密度高，耐高温性、耐腐蚀性、耐磨性良好，且复合涂层的润滑性能良好。本发明的合金刀具，具有良好的耐磨耐温性能。

Description

TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法 技术领域
本发明涉及硬质合金刀具技术领域，特别是涉及一种TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法。本申请是基于申请号2016100835077、申请日为2016年2月11日的中国发明专利申请为基础的。
背景技术
涂层硬质合金刀具的出现是刀具发展史上的一个重要里程碑。它是在强度和韧性较好的硬质合金基体上，利用气相沉积方法涂覆一薄层耐磨性好的难熔金属或非金属化合物而形成。
涂层作为一个化学屏障和热屏障，减少了刀具与工件间的扩散和化学反应，从而减少了月牙洼磨损。涂层具有很高的硬度和耐热性，并降低了刀具与工件间的摩擦系数，因此涂层刀具比未涂层刀具可显著地提高使用寿命，通常涂层刀具的寿命可比未涂层刀具高2-5倍。
硬质合金刀具在加工过程中承受极大的机械负荷和热负荷，极易产生磨损，从而影响其使用寿命，而对刀具材料进行表面改性，提高其表面性能，对提高刀具材料的使用寿命具有很重要的意义。在硬质合金表面涂上薄层的TiN、TiN、TiCN或Al2O3等高硬度耐磨材料，可提高刀具的耐磨性同时保持基体良好的韧性，可显著改善刀具材料的工作性能和使用寿命。然而涂层基本上为硬脆质材料，并且和硬质合金基体材料热膨胀系数不同，在涂层与基体之间的界面存在应力集中现象，通常裂纹容易在涂层表面产生并向合金内部扩散导致的材料失效。
TiN是最先被广泛使用的硬质涂层材料。TiN涂层性能优越，工艺过程又符合"绿色制造业"理念，但是TiN耐温有限，当使用温度超过500℃时抗氧化能力变差,仍限制了其应用领域。而随着技术的进步，人们对涂层的综合性能要求越来越高，并且对不同服役条件的产品，应该有特定表层性能的刀具基体与特定的复合涂层与之相适应，以增加涂层与基体之间的结合力和涂层的耐磨损性。
因此，针对现有技术不足，提供一种性能良好的TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法以克服现有技术不足甚为必要。
发明内容
本发明的目的之一在于避免现有技术的不足之处而提供一种TiAlSiZrN基复合涂层及其制备方法，TiAlSiZrN基复合涂层与刀具基体结合性良好，复合涂层的涂层之间附着力良好，致密度高，耐高温性、耐腐蚀性、耐磨性良好，且复合涂层的润滑性能良好。。
本发明的另一目的在于提供一种具有TiAlSiZrN基复合涂层的梯度超细 硬质合金刀具，具有良好的耐磨耐温性能。
本发明的上述目的通过如下技术手段实现。
提供一种TiAlSiZrN基复合涂层，包括用于沉积于刀具表面作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层，所述支撑层由TiN层和TiSiN层交替构成。
优选的，上述过渡层厚度为500-2000nm；所述支撑层的厚度为500-4000nm；所述耐磨层的厚度为500-4000nm；所述减磨层的厚度为500-4000nm；
所述支撑层中，单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
提供一种TiAlSiZrN基复合涂层的制备方法，采用电弧离子镀方法依次沉积作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层。
进一步的，所述过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉积的；
所述支撑层是在氮气环境下，气压O.5-2.3Pa、电压、150V-250V的条件下沉积的；
所述耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
所述减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的。
进一步的，上述的TiAlSiZrN基复合涂层的制备方法，制备过程如下，
(1)首先使电弧离子镀设备抽真空至1.52×10-2Pa以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置有遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
优选的，上述的TiAlSiZrN基复合涂层的制备方法，具体制备过程如下，
(1)首先使电弧离子镀设备抽真空至1.52×10-2Pa以下，然后加热炉体至500℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为2Pa，在温度为400℃的条件下，利用Ar离子辉光清洗基体30min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.5Pa，Ar+在1250V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
提供一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，由刀具基体和设置于刀具基体上的TiAlSiZrN基复合涂层构成；
所述刀具基体设置有正常组织层、富钴过渡层和贫钴富立方相层，所述正常组织层、富钴过渡层和贫钴富立方相层按照从内而外的顺序依次排列；
所述TiAlSiZrN基复合涂层由作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层构成，所述支撑层由TiN层和TiSiN层交替构成；
所述过渡层沉积于所述贫钴富立方相层表面。
进一步的，所述刀具基体中钴的含量为5-15wt.％；
所述正常组织层为超细硬质合金，WC晶粒尺寸为1-10000nm；
所述正常组织层的厚度大于2mm,所述富钴过渡层的厚度为20-100um；所述贫钴富立方相层的厚度为20-50um；
所述过渡层厚度为500-2000nm；所述支撑层的厚度为500-4000nm；所述耐磨层的厚度为500-4000nm；所述减磨层的厚度为500-4000nm；
所述支撑层中，单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
进一步的，所述刀具基体中钴的含量为8-12wt.％；
所述正常组织层为超细硬质合金，WC晶粒尺寸为1-400nm。
进一步的，上述的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，通过电弧离子镀方法将过渡层沉积于所述贫钴富立方相层，通过电弧离子镀方法将所述支撑层沉积于所述过渡层，通过电弧离子镀方法将耐磨层沉积于所述支撑层，通过电弧离子镀方法将所述减磨层沉积于所述耐磨层；
所述过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉积的；
所述支撑层是在氮气环境下，气压O.5-2.3Pa、电压、150V-250V的条件下沉积的；
所述耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
所述减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的。
进一步的，上述具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，TiAlSiZrN基复合涂层的制备过程如下，
(1)首先使电弧离子镀设备抽真空至1.4×10-2Pa以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
本发明的TiAlSiZrN基复合涂层，其与刀具基体结合性良好，复合涂层的涂层之间附着力良好，致密度高，耐高温性、耐腐蚀性、耐磨性良好，且复合涂层的润滑性能良好。具有该TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，具有良好的耐磨耐温性能。
附图说明
利用附图对本发明作进一步的说明，但附图中的内容不构成对本发明的任何限制。
图1是本发明一种TiAlSiZrN基复合涂层的层间结构示意图。
图2是本发明一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具的层间结构示意图。
图3是本发明一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具的示意图。
具体实施方式
结合以下实施例对本发明作进一步描述。
实施例1。
一种TiAlSiZrN基复合涂层，如图1所示，包括用于沉积于刀具表面作 为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层。
过渡层厚度为500-2000nm；支撑层的厚度为500-4000nm；耐磨层厚度为500-4000nm；减磨层厚度为500-4000nm。
具体的，支撑层由TiN层和TiSiN层交替构成，其中单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
该TiAlSiZrN基复合涂层，采用电弧离子镀方法依次沉积作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层。
其中，过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉积的；
支撑层是在氮气环境下，气压O.5-2.3Pa、电压、150V-250V的条件下沉积的；
耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的。
具体的制备过程如下：
(1)首先使电弧离子镀设备抽真空至以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，按照沉积条件依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2的状况下自然冷却至80℃以下。
从Ti靶上将Ti离子高温蒸发并在高偏压作用下高速运动到硬质合金刀片表面，在硬质合金刀片表面加有1000-1200V的负高压，高压对离化的Ti离子具有加速作用，经过加速的Ti离子会高速撞击硬质合金刀片表面，撞击过程会产生高温，Ti离子会与硬质合金刀片基体形成冶金结合层，一般扩散深度达到5-10nm Ti离子的轰击作用一是可以形成冶金结合层，二是可以 在硬质合金刀片的表面沉积纯Ti层，由于轰击和沉积过程同时进行，形成的Ti涂层会非常致密，抑制了柱状Ti粗晶粒的生长。然后通入氮气与Ti反应生成TiN过渡层。过渡层厚度一般为100-300纳米。在TiN涂层的基础上，逐步开启TiSi靶，TiSi与氮气反应生成TiSiN涂层，当合金刀运动到Ti靶前面时将形成TiN涂层，当运动到TiSi靶前部时将形成TiSiN涂层，合金刀连续的转动将会形成TiN/TiSiN纳米复合涂层作为支撑层。
将两者结合，不但使TiSiN和底层的TiN具有很好的结合力，同时在保持硬度的基础上大幅度降低了涂层内应力。支撑层厚度一般为500-1500nm。当支撑层沉积结束后，涂层具有了一定的厚度和硬度，为了提高其耐温性，关闭Ti靶，沉积具有良好耐温性能的纯的TiSiN涂层，TiSiN涂层中TiN纳米晶的大小对涂层硬度和耐温性具有较大的影响，为此必须控制TiN纳米晶的大小，一般控制在5-20纳米。
该复合涂层不但具有较好的耐磨性能，同时由于多层结构具有良好的耐腐蚀性能。与常规的单层TiN相比，由于TiSiN涂层材料的加入，使涂层不但具有良好的耐磨性能，同时其润滑性能大幅度上升。此外，TiN/TiSiN层梯度的设计为高硬度耐磨层提供了较好的支撑作用，使表面TiAlSiZrN复合耐磨层具有更好的耐磨效果。在TiN/TiSiN层的基础上，TiSiN纳米晶复合涂层的使用主要是为了在TiN层与TiSiN层之间、在TiSiN层与TiAlSiZrN层之间提供成分渐变，起到良好的降低应力的作用。在TiSiN涂层的基础上，沉积TiAlSiZrN层，形成TiSiN/TiAlSiZrN的层间结构层，TiAlSiZrN层不但具有高硬度，同时具有一定的减磨性能，降低复合涂层的摩擦系数，当加工各种材料时提供较好的润滑性能，提高加工效果。为此本涂层不但结构设计先进，同时多种材料的配合使用使涂层具有良好的适应性能。
本发明的复合涂层，用于沉积于硬质合金刀具基体表面，当其制备于硬质合金刀具基体表面时，与刀具基体结合性良好，所制备的刀具耐磨耐温性能良好，大幅度提高了硬质合金刀具的加工性能。
实施例2。
一种制备如实施例1的TiAlSiZrN基复合涂层的方法，具体制备过程如下，
(1)首先使电弧离子镀设备抽真空至以下，然后加热炉体至500℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为2Pa，在温度为400℃的条件下，利用Ar离子辉光清洗基体30min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.5Pa，Ar+在1250V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2快冷至80℃以下。
本实施例所制备的TiAlSiZrN基复合涂层，其与刀具基体结合性良好，复合涂层的涂层之间附着力良好，致密度高，耐高温性、耐腐蚀性、耐磨性良好，且复合涂层的润滑性能良好。具有该TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，具有良好的耐磨耐温性能。
实施例3。
一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，由刀具基体和设置于刀具基体上的TiAlSiZrN基复合涂层构成，如图2、图3所示。
刀具基体设置有正常组织层、富钴过渡层和贫钴富立方相层，正常组织层、富钴过渡层和贫钴富立方相层按照从内而外的顺序依次排列。刀具基体中钴的含量为5-15wt.％，优选钴的含量为8-12wt.％。正常组织层为超细硬质合金，WC晶粒尺寸为1-10000nm，优选WC晶粒尺寸为1-500nm。
贫钴富立方相层中富含立方相氮化物或碳氮化物，硬质合金中的立方相氮化物和碳氮化物具有比密排六方相的WC更高的硬度.因此，贫钴富立方相的表层具有更高的硬度。富钴过渡层中富含的粘结相，当涂层中形成的裂纹扩散到该区域时,由于其良好的韧性,可以吸收裂纹扩散时的能量,因此,能够有效地阻止裂纹向合金内部扩散，并且能较好地吸收刀具切削时的冲击能量，因而有高的抗冲击韧性特性，进而有利于提高刀具材料的使用寿命。芯部为刚性组织区域，即正常组织层，WC晶粒分布均匀且细小，平均WC晶粒尺寸≤500nm，具有超细硬质合金优异的力学性能。
TiAlSiZrN基复合涂层由作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层构成；过渡层沉积于贫钴富立方相层表面。
其中，正常组织层的厚度大于2mm,富钴过渡层的厚度为20-100um；贫钴富立方相层的厚度为20-50um。
过渡层厚度为500-2000nm；支撑层的厚度为500-4000nm；耐磨层厚度为500-4000nm；减磨层厚度为500-4000nm。
所述支撑层由TiN层和TiSiN层交替构成，其中单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
本发明的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，采用在表面贫钴富立方相层梯度超细硬质合金刀具基体上进行纳米多层复合涂层，可有效控制基体梯度和涂层的结构与成分，TiAlSiZrN基复合涂层与基体具有良好的结合力，所形成的刀具具有良好的耐磨耐温性能。
本发明的刀具基体从里到外由三层组成，分别为正常组织层、富钴过渡层、贫钴富立方相层。贫钴富立方相层中富含立方相氮化物或碳氮化物，硬质合金中的立方相氮化物和碳氮化物具有比密排六方相的WC更高的硬度。因 此，贫钴富立方相的表层具有更高的硬度；富钴过渡层中富含的粘结相，当涂层中形成的裂纹扩散到该区域时,由于其良好的韧性,可以吸收裂纹扩散时的能量,因此,能够有效地阻止裂纹向合金内部扩散，并且能较好地吸收刀具切削时的冲击能量，因而有高的抗冲击韧性特性，进而有利于提高刀具材料的使用寿命；芯部为刚性组织区域，WC晶粒分布均匀且细小(平均WC晶粒尺寸≤500nm)，刀具基体具有优异的力学性能。
本发明充分利用纳米晶非晶复合、纳米多层复合，梯度复合以及多层结构涂层技术，形成结构和成分渐变，涂层与基体、以及涂层间具有良好的附着力。
与常规电弧离子镀技术相比，本发明采用多层结构技术抑制了柱状晶的生长，提高了涂层的致密度，使得复合涂层的耐腐蚀性增强，同时耐磨性也大幅度提高，使得所制备的刀具具有良好的耐腐蚀性能和耐磨性能。
本发明通过设置耐温较好的TiSiN层和摩擦系数较低的TiAlSiZrN层构建新型的耐磨和自润滑涂层，突破现有刀具涂层润滑性能较差的缺点，所制备的刀具具有良好的润滑性能。
本发明的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，相对于普通硬质合金刀具，其切削性能得到了大幅提高。
实施例4。
一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其制备过程包括刀具基体的制备及在刀具基体表面沉积TiAlSiZrN基复合涂层。
具体制备过程如下：
(1)以难熔金属碳化物、粘结金属和TiCN和其他粉末如TiC,TaC,或其他强氮化物形成元素的碳化物、碳氮化物为原料，通过球磨混合、干燥过筛、压制成型和烧结四个步骤制备得到硬质合金基体前驱体；
(2)对硬质合金基体前驱体进行精磨加工处理；
(3)对精磨加工处理后的硬质合金基体前驱体进行梯度烧结，制备得到表层贫钴和富立方相梯度结构硬质合金刀具基体；
(4)对刀具基体进行化学清洗后，然后在其表面沉积过渡层，该过渡层为TiN层；过渡层用于增进与刀具基体的结合力，降低内应力；
(5)在上述得到的过渡层上沉积支撑层，支撑层为TiN/TiSiN层；支撑层用于提高韧性和强度；
(6)在上述得到的支撑层上层积耐磨层，耐磨层为TiSiN层；耐磨层用于提高硬度、强度和抗氧化性能；
(7)在上述得到的耐磨层上层积减磨层，减磨层层为TiAlSiZrN层；减磨层可以提高抗氧化性能，降低摩擦系数。
本实施例所制备的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，复合涂层与刀具基体结合性良好，该合金刀具具有耐高温性、耐腐蚀性、耐磨性良好，且复合涂层的润滑性能良好的特点。
实施例5。
一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其制备过程包括刀具基体的制备及在刀具基体表面沉积TiAlSiZrN基复合涂层。
刀具基体由以下质量百分比的各组分烧结而成：5-15％的TiC，2-5％的TaC，10-15％合金粘结相，余量为WC。合金粘结相由以下质量百分比的粉体组成：0.5-5.5％的Cr，0.5-5.5％的Mo，0.5-5.5％的B，0.5-5.5％的Al，0.5-5.5％的V，0.5-5.5％的Y，0.5-5.5％的Si，余量为Co，且合金粘结相中Cr、Mo、B、Al、V、Y和Si的质量之和为合金粘结相质量的7-20％。
刀具基体的制备方法，包括以下步骤：
S1、制备合金粘结相：按质量百分比分别称取Cr、Mo、B、Al、V、Y、Si、Co八种粉体，将八种粉体混合均匀，得合金粘结相。优选将八种粉体置于球磨机中，用硬质合金研磨球球磨72小时，且每球磨1h就暂停球磨10min，得到合金粘结相。
S2、制备坯料：按质量百分比分别称取合金粘结相、TiC、TaC、WC四种组分，四种组分组成原料粉体；按原料粉体总质量的1.5-2.5％称取石蜡，并将石蜡与原料粉体混合均匀，得到坯料。
S3、压制坯体：将坯料压制成型，得坯体。
可先用压模机将坯料压制成型，得初坯体；再用冷等静压机进一步压制初坯体，得坯体。
S4、烧结：将坯体置于烧结炉中，以5-8℃/min的速度升温至1200-1250℃，保温18-22min，并保持10-3Pa以下的真空度；然后向烧结炉中充入氮气并以1-3℃/min的速度升温至1420-1450℃，保温55-65min且保持0.2MPa以上的压强；接着再以2-6℃/min的速度降温至1000-1200℃，保温110-130min，并保持0.2MPa以上的压强；再接着坯体随炉冷却，并保持0.2MPa以上的压强，制得表面硬化的梯度硬质合金。
可在步骤S4前，进行预烧结步骤，所述预烧结步骤是将坯体置于烧结炉中，在惰性气体气氛下，以1400℃烧结10min；坯体随炉冷却后精修坯体外形。
该方法所制备的硬质合金基体具有优异的力学性能，改善了硬质合金的红硬性。硬质合金基体内的晶粒细小，硬质合金的表层富立方相而贫粘结相，并且表层下还有一富合金化粘结相的过度层，从而使硬质合金具有优异的硬度、耐磨性和韧性。
合金基体制备完成后，对其进行化学清洗，然后在其表面沉积TiAlSiZrN基复合涂层。
本实施例具体通过电弧离子镀方法将过渡层沉积于贫钴富立方相层，通过电弧离子镀方法将支撑层沉积于过渡层，通过电弧离子镀方法将耐磨层沉积于所述支撑层，通过电弧离子镀方法将所述减磨层沉积于所述耐磨层。
过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉 积的；
支撑层是在氮气环境下，气压O.5-2.3Pa、电压、150V-250V的条件下沉积的；
耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的。
TiAlSiZrN基复合涂层的沉积过程，具体如下，
(1)首先使电弧离子镀设备抽真空至以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
(2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
(3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
(4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
(5)复合涂层完毕后，于真空状况或通入H2自然冷却至80℃以下。
本发明的所制备的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，采用在表面贫钴富立方相层梯度超细硬质合金刀具基体上进行纳米多层复合涂层，可有效控制基体梯度和涂层的结构与成分，TiAlSiZrN基复合涂层与基体具有良好的结合力，所形成的刀具具有良好的耐磨耐温性能。
本发明的刀具基体刀具基体具有优异的力学性能，复合涂层与基体、以及涂层间具有良好的附着力，刀具耐腐蚀性能、耐摩擦性能及自润滑性能良好。
本发明所制备的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，相对于普通硬质合金刀具，其切削性能得到了大幅提高。
最后应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种TiAlSiZrN基复合涂层，其特征在于：包括用于沉积于刀具表面作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层，所述支撑层由TiN层和TiSiN层交替构成。
  2. 根据权利要求1所述的TiAlSiZrN基复合涂层，其特征在于：所述过渡层厚度为500-2000nm；所述支撑层的厚度为500-4000nm；所述耐磨层的厚度为500-4000nm；所述减磨层的厚度为500-4000nm；
    所述支撑层中，单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
  3. 一种TiAlSiZrN基复合涂层的制备方法，其特征在于：采用电弧离子镀方法依次沉积作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层。
  4. 根据权利要求3所述的TiAlSiZrN基复合涂层的制备方法，其特征在于：
    所述过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉积的；
    所述支撑层是在氮气环境下，气压O.5-2.3Pa、电压150V-250V的条件下沉积的；
    所述耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
    所述减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的。
  5. 根据权利要求4所述的TiAlSiZrN基复合涂层的制备方法，其特征在于：制备过程如下，
    (1)首先使电弧离子镀设备抽真空至1.52×10-2Pa以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
    (2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置有遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
    (3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
    (4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
    (5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
  6. 根据权利要求5所述的TiAlSiZrN基复合涂层的制备方法，其特征在于：具体制备过程如下，
    (1)首先使电弧离子镀设备抽真空至1.52×10-2Pa以下，然后加热炉体至500℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
    (2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为2Pa，在温度为400℃的条件下，利用Ar离子辉光清洗基体30min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
    (3)增加Ar+流量至3.5Pa，Ar+在1250V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
    (4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
    (5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
  7. 一种具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其特征在于：
    由刀具基体和设置于刀具基体上的TiAlSiZrN基复合涂层构成；
    所述刀具基体包括正常组织层、富钴过渡层和贫钴富立方相层，所述正常组织层、富钴过渡层和贫钴富立方相层按照从内而外的顺序依次排列；
    所述TiAlSiZrN基复合涂层由作为过渡层的TiN层、沉积于过渡层上作为支撑层的TiN/TiSiN层、沉积于支撑层上作为耐磨层的TiSiN层和沉积于耐磨层上作为减磨层的TiAlSiZrN层构成，所述支撑层由TiN层和TiSiN层交替构成；
    所述过渡层沉积于所述贫钴富立方相层表面。
  8. 根据权利要求7所述的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其特征在于：
    所述刀具基体中钴的含量为5-15wt.％；
    所述正常组织层为超细硬质合金，WC晶粒尺寸为1-10000nm；
    所述正常组织层的厚度大于2mm,所述富钴过渡层的厚度为20-100um；所述贫钴富立方相层的厚度为20-50um；
    所述过渡层厚度为500-2000nm；所述支撑层的厚度为500-4000nm；所述耐磨层的厚度为500-4000nm；所述减磨层的厚度为500-4000nm；
    所述支撑层中，单层TiSiN层的厚度为9-15nm，单层TiSiN层的厚度为8-16nm，相邻两层TiSiN层和TiN层的厚度之和为17-31nm。
  9. 根据权利要求8所述的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其特征在于：
    所述刀具基体中钴的含量为8-12wt.％；
    所述正常组织层的WC晶粒尺寸为1nm-400nm。
  10. 根据权利要求9所述的具有TiAlSiZrN基复合涂层的梯度超细硬质合金刀具，其特征在于：
    通过电弧离子镀方法将过渡层沉积于所述贫钴富立方相层，通过电弧离子镀方法将所述支撑层沉积于所述过渡层，通过电弧离子镀方法将耐磨层沉积于所述支撑层，通过电弧离子镀方法将所述减磨层沉积于所述耐磨层；
    所述过渡层是在氮气环境下，气压O.1-0.5Pa、电压100V-250V的条件下沉积的；
    所述支撑层是在氮气环境下，气压O.5-2.3Pa、电压150V-250V的条件下沉积的；
    所述耐磨层是在氮气环境下，气压O.l-lPa、电压150V-250V的条件下沉积的；
    所述减磨层是在氮气环境下，气压O.l-0.5Pa、电压150V-250V的条件下沉积的；
    所述TiAlSiZrN基复合涂层的制备过程如下，
    (1)首先使电弧离子镀设备抽真空至1.4×10-2Pa以下，然后加热炉体至450-550℃，并保持电弧离子镀设备抽真空且内部气压不大于10-3Pa；
    (2)通入纯度为99.999％的高纯度Ar气，在Ar流量为260SCCM时保持压强为1.8-2.5Pa，在温度为380-450℃的条件下，利用Ar离子辉光清洗基体25-35min；在Ar离子辉光清洗基体的过程中，初始脉冲偏压为-600V、占空比为30％，在三分钟内，使得脉冲偏压达到-1000V、占空比达到50％；靶材和基体中间放置遮挡板，避免靶材清洗过程中轰击出的靶材原子沉积在基体上；
    (3)增加Ar+流量至3.0-4.0Pa，Ar+在1200V-1300V的基体偏压下获得高的粒子能量以轰击、侵烛基体，去除基体表面杂质；
    (4)移开遮挡板，依次沉积制备过渡层、支撑层、耐磨层和减磨层；
    (5)复合涂层完毕后，于真空状况或通入H2状况下自然冷却至80℃以下。
PCT/CN2016/075350 2016-02-11 2016-03-02 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法 Ceased WO2017136970A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610083507.7A CN105624618B (zh) 2016-02-11 2016-02-11 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN201610083507.7 2016-02-11

Publications (1)

Publication Number Publication Date
WO2017136970A1 true WO2017136970A1 (zh) 2017-08-17

Family

ID=56039956

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/075350 Ceased WO2017136970A1 (zh) 2016-02-11 2016-03-02 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法

Country Status (2)

Country Link
CN (1) CN105624618B (zh)
WO (1) WO2017136970A1 (zh)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111014616A (zh) * 2019-12-26 2020-04-17 爱柯迪股份有限公司 HfZrWMoVNbN/CrSiN高熵合金纳米复合涂层压铸铝模具及其制备方法
CN112628381A (zh) * 2020-12-02 2021-04-09 东南大学 一种温度自适应润滑齿轮及其制备方法
CN113913739A (zh) * 2021-10-09 2022-01-11 北京市辐射中心 凿岩机冲击器活塞表面Ti-N基超硬自润滑涂层的制备方法
CN114318467A (zh) * 2022-01-17 2022-04-12 西安工业大学 一种适用于海洋环境下钛合金耐磨损、抗菌复合涂层及其制备方法
CN114807872A (zh) * 2022-04-29 2022-07-29 江西省科学院应用物理研究所 一种高熵合金/Ti3SiC2多层复合涂层及其制备方法
CN114941126A (zh) * 2022-06-29 2022-08-26 武汉苏泊尔炊具有限公司 抗菌刀具及其制造方法
CN114941123A (zh) * 2022-06-13 2022-08-26 上海锐畅医疗科技有限公司 一种医疗器械用多元氮化物复合涂层及其制备方法
CN115110033A (zh) * 2022-07-27 2022-09-27 南京真合材料科技有限公司 一种超硬膜层制造方法
CN115142019A (zh) * 2022-07-11 2022-10-04 中国建筑土木建设有限公司 用于盾构机的刀具及其制备方法
CN115595538A (zh) * 2022-10-17 2023-01-13 贵州永红航空机械有限责任公司（Cn） 不锈钢列管式散热器表面TiAlN膜层的制备方法
CN117070886A (zh) * 2023-08-31 2023-11-17 上海应用技术大学 一种TiZrAlSiN复合梯度薄膜及其制备方法
CN117344274A (zh) * 2023-10-18 2024-01-05 株洲瑞德尔智能装备有限公司 一种AlTiN复合涂层的制备方法和涂层刀具
CN117626182A (zh) * 2023-11-30 2024-03-01 厦门九牧研发有限公司 一种多层复合镀层及其制备方法和产品
CN117821913A (zh) * 2024-03-06 2024-04-05 欧优格(大连)切削工具有限公司 一种应用于合金刀具的多层多元纳米复合硬质涂层
CN119020734A (zh) * 2024-08-14 2024-11-26 广东工业大学 一种纳米多层梯度异质复合涂层及其制备方法和应用
CN119491200A (zh) * 2025-01-13 2025-02-21 赣州澳克泰工具技术有限公司 一种具有高硬度自润滑涂层的切削刀具及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105624618B (zh) * 2016-02-11 2018-01-19 广东工业大学 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN109576643A (zh) * 2018-12-27 2019-04-05 科汇纳米技术（深圳）有限公司 一种TiSiVN多组元复合梯度刀具涂层及其制备方法
CN110343993A (zh) * 2019-08-07 2019-10-18 广东工业大学 一种硬质合金表面处理方法及应用
CN113529080B (zh) * 2021-07-19 2023-03-31 厦门鸿鹭联创工具有限公司 一种用于pcb微型铣刀的涂层
CN115418608B (zh) * 2022-08-26 2023-10-20 广东工业大学 一种TiN-TiN/TiSiN-TiSiN纳米多层梯度复合涂层及其制备方法和应用
CN117344107B (zh) * 2023-09-14 2024-09-10 成都飞机工业（集团）有限责任公司 一种应用于苛刻工况的复合润滑涂层及其制备和使用方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001269801A (ja) * 2000-03-23 2001-10-02 Mitsubishi Materials Corp 硬質被覆層がすぐれた耐熱塑性変形性を発揮する表面被覆超硬合金製切削工具
CN1455017A (zh) * 2003-05-29 2003-11-12 四川大学 表面层贫钴的梯度硬质合金上进行金刚石涂层的方法
US20050109607A1 (en) * 2003-11-20 2005-05-26 Ehiasarian Arutiun P. Combined coating process comprising magnetic field-assisted, high-power, pulsed cathode sputtering and an unbalanced magnetron
CN101974713A (zh) * 2010-10-25 2011-02-16 北京科技大学 一种脱β层梯度硬质合金的制备方法
CN102166849A (zh) * 2010-12-20 2011-08-31 武汉新铬涂层设备有限公司 氮化铬铝钛复合涂层、沉积有该涂层的刀具及制备方法
CN103056425A (zh) * 2013-02-27 2013-04-24 武汉大学 一种超硬纳米晶TiN-CN-DLC梯度复合涂层合金钻头及其制备方法
CN103084600A (zh) * 2013-02-27 2013-05-08 武汉大学 超硬TiN-TiSiN-CN多层交替复合梯度涂层硬质合金刀片及制备方法
CN104060230A (zh) * 2014-04-25 2014-09-24 湛江师范学院 一种TiZrAlSiON纳米复合超硬涂层刀具及其制备方法
CN105624618A (zh) * 2016-02-11 2016-06-01 广东工业大学 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE526336C2 (sv) * 2002-07-01 2005-08-23 Seco Tools Ab Skär med slitstark refraktär beläggning av MAX-fas
WO2010150335A1 (ja) * 2009-06-22 2010-12-29 株式会社タンガロイ 被覆立方晶窒化硼素焼結体工具
JP5490158B2 (ja) * 2012-02-03 2014-05-14 三菱重工業株式会社 表面被覆材料及びこれを利用する切削工具並びに工作機械
CN104160060A (zh) * 2012-03-07 2014-11-19 山高刀具公司 具有金属基氮化物层的刀体和涂布该刀体的方法
EP2636764B1 (en) * 2012-03-07 2014-07-09 Seco Tools Ab Nanolaminated coated cutting tool
CN104988373B (zh) * 2015-08-06 2017-08-08 广东工业大学 一种表面硬化的梯度硬质合金及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001269801A (ja) * 2000-03-23 2001-10-02 Mitsubishi Materials Corp 硬質被覆層がすぐれた耐熱塑性変形性を発揮する表面被覆超硬合金製切削工具
CN1455017A (zh) * 2003-05-29 2003-11-12 四川大学 表面层贫钴的梯度硬质合金上进行金刚石涂层的方法
US20050109607A1 (en) * 2003-11-20 2005-05-26 Ehiasarian Arutiun P. Combined coating process comprising magnetic field-assisted, high-power, pulsed cathode sputtering and an unbalanced magnetron
CN101974713A (zh) * 2010-10-25 2011-02-16 北京科技大学 一种脱β层梯度硬质合金的制备方法
CN102166849A (zh) * 2010-12-20 2011-08-31 武汉新铬涂层设备有限公司 氮化铬铝钛复合涂层、沉积有该涂层的刀具及制备方法
CN103056425A (zh) * 2013-02-27 2013-04-24 武汉大学 一种超硬纳米晶TiN-CN-DLC梯度复合涂层合金钻头及其制备方法
CN103084600A (zh) * 2013-02-27 2013-05-08 武汉大学 超硬TiN-TiSiN-CN多层交替复合梯度涂层硬质合金刀片及制备方法
CN104060230A (zh) * 2014-04-25 2014-09-24 湛江师范学院 一种TiZrAlSiON纳米复合超硬涂层刀具及其制备方法
CN105624618A (zh) * 2016-02-11 2016-06-01 广东工业大学 TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111014616A (zh) * 2019-12-26 2020-04-17 爱柯迪股份有限公司 HfZrWMoVNbN/CrSiN高熵合金纳米复合涂层压铸铝模具及其制备方法
CN112628381A (zh) * 2020-12-02 2021-04-09 东南大学 一种温度自适应润滑齿轮及其制备方法
CN112628381B (zh) * 2020-12-02 2022-05-10 东南大学 一种温度自适应润滑齿轮及其制备方法
CN113913739B (zh) * 2021-10-09 2024-03-08 北京市辐射中心 凿岩机冲击器活塞表面Ti-N基超硬自润滑涂层的制备方法
CN113913739A (zh) * 2021-10-09 2022-01-11 北京市辐射中心 凿岩机冲击器活塞表面Ti-N基超硬自润滑涂层的制备方法
CN114318467A (zh) * 2022-01-17 2022-04-12 西安工业大学 一种适用于海洋环境下钛合金耐磨损、抗菌复合涂层及其制备方法
CN114318467B (zh) * 2022-01-17 2023-09-12 西安工业大学 一种适用于海洋环境下钛合金耐磨损、抗菌复合涂层及其制备方法
CN114807872A (zh) * 2022-04-29 2022-07-29 江西省科学院应用物理研究所 一种高熵合金/Ti3SiC2多层复合涂层及其制备方法
CN114941123A (zh) * 2022-06-13 2022-08-26 上海锐畅医疗科技有限公司 一种医疗器械用多元氮化物复合涂层及其制备方法
CN114941123B (zh) * 2022-06-13 2024-03-08 上海锐畅医疗科技有限公司 一种医疗器械用多元氮化物复合涂层及其制备方法
CN114941126A (zh) * 2022-06-29 2022-08-26 武汉苏泊尔炊具有限公司 抗菌刀具及其制造方法
CN114941126B (zh) * 2022-06-29 2023-08-25 武汉苏泊尔炊具有限公司 抗菌刀具及其制造方法
CN115142019A (zh) * 2022-07-11 2022-10-04 中国建筑土木建设有限公司 用于盾构机的刀具及其制备方法
CN115110033B (zh) * 2022-07-27 2024-01-23 南京真合材料科技有限公司 一种超硬膜层制造方法
CN115110033A (zh) * 2022-07-27 2022-09-27 南京真合材料科技有限公司 一种超硬膜层制造方法
CN115595538A (zh) * 2022-10-17 2023-01-13 贵州永红航空机械有限责任公司（Cn） 不锈钢列管式散热器表面TiAlN膜层的制备方法
CN117070886A (zh) * 2023-08-31 2023-11-17 上海应用技术大学 一种TiZrAlSiN复合梯度薄膜及其制备方法
CN117344274A (zh) * 2023-10-18 2024-01-05 株洲瑞德尔智能装备有限公司 一种AlTiN复合涂层的制备方法和涂层刀具
CN117626182A (zh) * 2023-11-30 2024-03-01 厦门九牧研发有限公司 一种多层复合镀层及其制备方法和产品
CN117821913A (zh) * 2024-03-06 2024-04-05 欧优格(大连)切削工具有限公司 一种应用于合金刀具的多层多元纳米复合硬质涂层
CN119020734A (zh) * 2024-08-14 2024-11-26 广东工业大学 一种纳米多层梯度异质复合涂层及其制备方法和应用
CN119491200A (zh) * 2025-01-13 2025-02-21 赣州澳克泰工具技术有限公司 一种具有高硬度自润滑涂层的切削刀具及其制备方法

Also Published As

Publication number Publication date
CN105624618A (zh) 2016-06-01
CN105624618B (zh) 2018-01-19

Similar Documents

Publication Publication Date Title
CN105624618B (zh) TiAlSiZrN基复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN105603387B (zh) 氮化硼系复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN105586572B (zh) (Ti,Al,Zr)N多组元复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN109161711B (zh) 一种表面具有双梯度层结构的超细晶梯度硬质合金及其制备方法
CN105671551B (zh) 金刚石复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN107130221B (zh) 一种硬质合金多层梯度稀土复合涂层的制备方法
CN105463388B (zh) 氧化铝系复合涂层、具有该复合涂层的梯度超细硬质合金刀具及其制备方法
CN113564399B (zh) 一种梯度结构TiCN基金属陶瓷及提高其涂层结合力的方法
JP2020132972A (ja) 超硬合金および切削工具
JP2009034811A (ja) 突切り、溝切りおよびねじ切りのための超硬合金インサート
JP5555835B2 (ja) 耐摩耗性にすぐれたターニング加工用表面被覆切削工具およびその製造方法
CN110284038A (zh) 一种具有强(111)织构的pvd涂层及其制备方法
JP2011156645A (ja) 耐熱塑性変形性にすぐれる表面被覆ｗｃ基超硬合金製切削工具
JP5003308B2 (ja) 表面被覆切削工具
JP2008296292A (ja) 硬質被覆層がすぐれた耐欠損性を発揮する表面被覆切削工具
JP4281666B2 (ja) 金属粉末の高速プレス成形加工で潤滑性非晶質炭素系被膜がすぐれた耐摩耗性を発揮する表面被覆超硬合金製金型
JP5555834B2 (ja) 耐摩耗性にすぐれたミーリング加工用表面被覆切削工具およびその製造方法
JP7380219B2 (ja) 硬質被覆層がすぐれた耐チッピング性を発揮する表面被覆ＴｉＮ基サーメット製切削工具
JP2011088253A (ja) 耐熱塑性変形性に優れたｗｃ基超硬合金製切削工具および表面被覆ｗｃ基超硬合金製切削工具
JP2017179474A (ja) 非金属系材料を加工するための工具に用いる超硬合金
JP2009072837A (ja) 高速ミーリング加工で硬質被覆層がすぐれた耐摩耗性を発揮する表面被覆切削工具およびその製造方法
CN118814112B (zh) 复合构件及其制备方法
JP4126451B2 (ja) 超硬合金
CN110541102A (zh) 一种直接涂覆cbn涂层的涂层梯度硬质合金刀具及其制备方法
JP2010207930A (ja) 表面被覆切削工具

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16889699

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 16889699

Country of ref document: EP

Kind code of ref document: A1