CN111945111A - Composite coating deposited on surface of cubic boron nitride cutter and deposition method - Google Patents

Composite coating deposited on surface of cubic boron nitride cutter and deposition method Download PDF

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CN111945111A
CN111945111A CN202010880691.4A CN202010880691A CN111945111A CN 111945111 A CN111945111 A CN 111945111A CN 202010880691 A CN202010880691 A CN 202010880691A CN 111945111 A CN111945111 A CN 111945111A
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layer
cutter
composite coating
composite
boron nitride
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李鹏亮
白敬勇
孙斌
葛强
洪荣华
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Ws Precision Tools Shanghai Co ltd
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Ws Precision Tools Shanghai Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • 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
    • C23C14/0676—Oxynitrides
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    • 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
    • C23C14/08—Oxides
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    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/541—Heating or cooling of the substrates
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/548—Controlling the composition
    • 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
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks

Abstract

The invention relates to a composite coating deposited on the surface of a cubic boron nitride cutter and a deposition method, wherein the composite coating comprises a plurality of sub-coatings which are sequentially deposited from the side of a cutter substrate to the outer side, and each sub-coating at least comprises an Al-Cr-N layer, a middle transition layer and an Al-Cr-O composite oxide layer which are sequentially deposited from the side of the cutter substrate to the outer side; the Al-Cr-N layer is AlxCr1‑xN layer, wherein x is more than or equal to 0.1 and less than or equal to 0.3, and the intermediate transition layer is AlCrN-AlCrON- (AlCr)2O3A transition layer; the Al-Cr-O composite oxide layer is (Al)yCr1‑y)2O3Layer, wherein y is more than or equal to 0.1 and less than or equal to 0.3. The quick abrasion of the cutter under the high-temperature action formed by the accumulation of cutting heat under the working condition of high-speed dry cutting is solved, and the service life of the cutter is prolonged.

Description

Composite coating deposited on surface of cubic boron nitride cutter and deposition method
Technical Field
The invention relates to the technical field of cubic boron nitride cutter surface coatings, in particular to a composite coating deposited on the surface of a cubic boron nitride cutter and a deposition method.
Background
Among various hard coatings for tools in the metal working industry, aluminum oxide (Al)2O3) The high-speed dry cutting method has the advantages of being good in heat insulation capability, high-temperature hardness, oxidation resistance and chemical stability, capable of effectively blocking element diffusion and chemical abrasion between the cutter and a processed material at high temperature, and capable of achieving optimal hard coating component selection by cutting and grinding, and the high-speed dry cutting method is used for high-speed dry cutting of a cubic boron nitride (CBN/PCBN) cutter on hardened steel materials in industries such as bearing gears and the like.
However, due to Al2O3The evaporation source target material belongs to an insulating material, and oxygen ionized by plasma is easy to react with pure aluminum or aluminum alloy in the cathode target material to generate insulating aluminum oxide in the preparation process of Physical Vapor Deposition (PVD) coating, so that cathode discharge failure is caused, required aluminum and alloy elements cannot be normally output, and the evaporation source target material is poisoned. Moreover, positive charges are accumulated on the cathode surface during vacuum dc sputtering, and when the potential between the positive charges accumulated on the alumina layer and the negative potential target is sufficiently large, the alumina layer is broken down or discharge occurs along the edge thereof. Frequent abnormal discharges cause the power supply to constantly trip over load, so that the deposition process cannot be continued.
At the same time, Al2O3The difference in crystal structure and thermal expansion coefficient from other ceramics or metals also makes the bonding between cemented carbide and CBN tool surfaces very poor. These factors make the preparation and application of alumina coatings extremely difficult.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a composite coating deposited on the surface of a cubic boron nitride cutting tool and a deposition method thereof, which can solve the problem of rapid wear of the cutting tool under the high temperature action caused by the accumulation of cutting heat under the working condition of high-speed dry cutting and improve the service life of the cutting tool.
In order to achieve the purpose, the invention adopts the following technical scheme:
as one aspect of the present invention, a composite coating deposited on the surface of a cubic boron nitride tool, the composite coating comprising a plurality of sub-composite coatings deposited in sequence from the side of a tool substrate to the outside, each sub-composite coating comprising at least an Al-Cr-N layer, an intermediate transition layer, and an Al-Cr-O composite oxide layer deposited in sequence from the side of the tool substrate to the outside; the Al-Cr-N layer is AlxCr1-xN layer, wherein x is more than or equal to 0.1 and less than or equal to 0.3, and the intermediate transition layer is AlCrN-AlCrON- (AlCr)2O3A transition layer; the Al-Cr-O composite oxide layer is (Al)yCr1-y)2O3Layer, wherein y is more than or equal to 0.1 and less than or equal to 0.3.
In one embodiment, the thickness of the Al-Cr-N layer is 0.2 to 0.4 μm, the thickness of the intermediate transition layer is 0.1 to 0.2 μm, and the thickness of the Al-Cr-O composite oxide layer is 0.2 to 0.4 μm.
In one embodiment, the thickness of the composite coating is 1.5-6 μm.
As a second aspect of the invention, the method for depositing the composite coating on the surface of the cubic boron nitride cutter by adopting a physical vapor deposition method comprises the following steps:
firstly, cleaning and removing water-based and/or hydrocarbon-based pollutants on the surface of a cutter base material;
secondly, heating, vacuumizing and removing gas impurities at the welding seam part of the cutter;
thirdly, plasma etching is carried out, and the tool base material is subjected to activation treatment;
fourthly, heating, introducing nitrogen, using Al/Cr composite target material, adopting a direct current multi-arc method to deposit and form Al on the cutter base materialxCr1-xN layers;
the fifth stepGradually reducing the nitrogen flow to 0, simultaneously gradually increasing the oxygen flow from 0, introducing argon, starting a high-frequency high-energy pulse magnetic control power supply, adopting an unbalanced magnetic control and asymmetric high-frequency pulse method, wherein the ratio of the positive pulse width to the negative pulse width of the asymmetric high-frequency pulse is 1: 9-1: 20, and performing Al-phase magnetic control on AlxCr1-xThe surface of the N layer forms AlCrN-AlCrON- (AlCr)2O3The intermediate transition layer of (3);
sixthly, continuously introducing oxygen, continuously adopting a non-equilibrium magnetic control combined asymmetric high-frequency pulse method to form (Al) on the surface of the intermediate transition layeryCr1-y)2O3A layer;
and seventhly, repeating the fourth step to the sixth step until the thickness of the composite coating on the base material reaches the preset thickness.
The fourth step is specifically as follows: heating the cutter base material to 600-650 ℃, keeping the nitrogen flow at 3000-3500 sccm, adopting a 70 at% Al/30 at% Cr composite target material as the Al/Cr composite target material, keeping the target current at 150-180A, and keeping the base material biased at 30-36V to form Al on the cutter base materialxCr1-xAnd N layers.
The fifth step is specifically as follows: the nitrogen flow is adjusted to be gradually reduced to 0 from 3000-3500 sccm, the oxygen flow is gradually increased to 3000-3500 sccm from 0, the argon flow is 500-1000 sccm, the magnetic control magnetic field intensity is 320-400 gauss, the power of high-frequency high-energy pulse is 10-15 kW, the frequency is 25-50 kHZ, the voltage is 24-40V, the negative pulse width is 36-40 mus, the positive pulse width is 2-4 mus, the target current is 150-180A, the base material bias voltage is 30-36V, and Al is addedxCr1-xThe surface of the N layer forms AlCrN-AlCrON- (AlCr)2O3The intermediate transition layer of (3).
The sixth step is specifically as follows: maintaining oxygen flow of 3000-3500 sccm, argon flow of 500-1000 sccm, power of high-frequency high-energy pulse of 10-15 kW, frequency of 25-50 kHz, voltage of 24-40V, negative pulse width of 36-40 mus, positive pulse width of 2-4 mus, target current of 150-180A, substrate bias voltage of 30-36V, forming a surface layer of an intermediate transition layer (Al isyCr1-y)2O3And (3) a layer.
As a third aspect of the present invention, a method for depositing a sub-composite coating on a surface of a cubic boron nitride cutting tool using a vacuum deposition apparatus, the sub-composite coating comprising an Al-Cr-N layer, an intermediate transition layer and an Al-Cr-O composite oxide layer deposited in this order from a side of a cutting tool base body to an outer side, the intermediate transition layer being a transition layer from AlCrN to AlCrON to AlCrO, is characterized in that: the sub-composite coating is deposited on the surface of the cubic boron nitride cutter base material by an evaporation source, the evaporation source comprises a first group of evaporation sources operated by a direct-current multi-arc power supply and a second group of evaporation sources operated by a high-frequency high-energy pulse magnetic control power supply, the target materials of the first group of evaporation sources and the second group of evaporation sources are Al/Cr composite target materials, and the evaporated Al and Cr react on the surface of the cutter base material in a nitrogen-containing reaction gas environment to form the Al-Cr-N layer by arc discharge generated by the direct-current multi-arc power supply; the non-equilibrium magnetic control multi-arc and asymmetric high-frequency pulse generated by the high-frequency high-energy pulse magnetic control power supply react evaporated Al and Cr on the surface of the Al-Cr-N layer in a nitrogen and/or oxygen-containing reaction gas environment to form a middle transition layer and an Al-Cr-O composite oxide layer in sequence.
Wherein the Al-Cr-N layer is AlxCr1-xN layer, wherein x is more than or equal to 0.1 and less than or equal to 0.3, and the intermediate transition layer is AlCrN-AlCrON- (AlCr)2O3A transition layer; the Al-Cr-O composite oxide layer is (Al)yCr1-y)2O3Layer, wherein y is more than or equal to 0.1 and less than or equal to 0.3.
Wherein the ratio of the positive pulse width to the negative pulse width of the asymmetric high-frequency pulse is 1: 9-1: 20.
The invention has the following beneficial effects:
the high-energy pulse magnetron sputtering (HIPMS) is based on the traditional direct-current multi-arc sputtering, and a narrow forward pulse voltage is superposed on the original pure direct-current negative pressure waveform, so that the voltage waveform applied to the target material is changed into a pulse wave with asymmetric positive and negative half cycles. In a wider negative pulse half period, positive ions in the discharge plasma fly to the target to form target sputtering; during the positive pulse, the particles (mainly electrons) with negative charges in the discharge plasma fly to the target to neutralize the positive charges accumulated on the alumina insulating layer on the target surface, thereby eliminating the cause of abnormal discharge. This function of high frequency, high energy pulses ensures that sputter deposition can be carried out stably for long periods of time.
Therefore, the difficult problem that the alumina coating with the heat insulation corundum structure can not be smoothly and continuously deposited is solved, the Al/Cr nitride bottom coating with good bonding property with the cutter base material is combined, and the interlayer bonding of the heat insulation coating and the toughness of the composite coating are ensured through the transition from the Al/Cr nitrogen oxide to the Al/Cr nitride layer. The coating with the components and the structure is beneficial to resisting the rapid abrasion of the cutter under the high-temperature action formed by the accumulation of cutting heat under the working condition of high-speed dry cutting, and the service life of the cutter is prolonged.
Drawings
FIG. 1 is a schematic view of the overall structure of a vacuum coating apparatus according to the present invention;
FIG. 2 is a schematic structural view of a composite coating of the present invention;
FIG. 3 is a comparison of the surface topography of DC multi-arc and magnetron sputtering coatings;
FIG. 4 is a schematic diagram of the period of the high frequency high energy pulse.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
fig. 1 shows a vacuum coating apparatus 1, wherein the vacuum coating apparatus 1 comprises a PVD chamber 11, a first set of evaporation sources 13 operated by a dc multi-arc power supply 12 respectively are arranged in the PVD chamber 11, and the first set of evaporation sources 13 comprises a first target 131, a first cooling plate 132 located below the first target 131, and first grounded anodes 133 coupled to both sides of the first target 131; a second group of evaporation sources 15 operated by a high-energy high-frequency pulse magnetron power supply 14 is also arranged, wherein the second group of evaporation sources 15 comprises a second target 151, a high-strength permanent magnet system 152 and a second cooling plate 153 which are positioned below the second target 151, and second grounding anodes 154 which are connected to two sides of the second target 151. The first target 131 and the second target 151 are both Al/Cr composite targets.
A first gas inlet 161 is opened between two evaporation sources of the first group of evaporation sources 13 of the PVD furnace chamber 11, and reaction gases such as nitrogen and oxygen are introduced into the PVD furnace chamber 11 through the first gas inlet 161. A second gas inlet 162 is opened between two evaporation sources of the second group of evaporation sources 15 of the PVD furnace chamber 11, and additional reaction gas such as argon is introduced into the PVD furnace chamber 11 through the second gas inlet 162. The vacuum coating device 1 is also provided with a plasma source 17, and ionizes additional reaction gas such as inert argon gas to generate argon ions to bombard a workpiece needing coating, and activates a cutter base material to improve the film adhesion.
A gas outlet 163 is formed at one side of the PVD chamber 11, and the gas outlet 163 is connected to a pump system 164 for generating a desired vacuum in the PVD chamber 11. The inside of the PVD furnace chamber 11 is provided with a workpiece fixture 18 for fixing the workpiece for coating on the workpiece. A medium frequency bias voltage source 181 is electrically connected to the workpiece fixture 18 for applying a base voltage or bias voltage to the workpiece.
By utilizing the vacuum coating device 1, a composite coating 2 can be deposited on a workpiece fixed on the workpiece fixing device 18, in particular a composite coating 2 is deposited on the surface of a cubic boron nitride (CBN/PCBN) cutter, and the composite coating 2 solves the problem of rapid abrasion of the cutter under the high-temperature action formed by accumulation of cutting heat under the working condition of high-speed dry cutting, and prolongs the service life of the cutter.
Specifically, the thickness of the composite coating 2 is preferably 1.5-6 μm. Referring to fig. 2, the composite coating 2 comprises a plurality of sub-composite coatings 20 deposited from the side of the cutter substrate 10 to the outside in sequence, and each sub-composite coating 20 at least comprises an Al-Cr-N layer 21, an intermediate transition layer 22 and an Al-Cr-O composite oxide layer 23 deposited from the side of the cutter substrate 10 to the outside in sequence.
The Al-Cr-N layer 21 is AlxCr1-xAnd the X is more than or equal to 0.1 and less than or equal to 0.3, the Cr-containing Al-Cr-N layer 21 has good toughness, the bonding property with the cutter substrate 10 material is improved, and particularly, the thickness of the Al-Cr-N layer 21 is 0.2-0.4 mu m. The intermediate transition layer 22 is deposited on AlxCr1-xThe surface of the N layer is formed with 0.1-0.2 μm AlCrN-AlCrON- (AlCr)2O3The transition layer realizes the composition and structure transition from nitride to oxide and further increases the bonding force of the oxide coating. The Al-Cr-O composite oxide layer 23 is deposited on the surface of the intermediate transition layer 22 and comprises the component (Al)yCr1-y)2O3Wherein y is more than or equal to 0.1 and less than or equal to 0.3, and specifically, the thickness of the Al-Cr-O composite oxide layer 23 is 0.2-0.4 μm.
The following describes the method and steps for depositing the composite coating 2 on the surface of a cubic boron nitride (CBN/PCBN) cutting tool, as follows:
in the first step, the tool is cleaned in order to remove water-based and/or hydrocarbon-based surface contaminants such as oil stains and scale.
And secondly, purging argon in the PVD furnace chamber, heating to 250-400 ℃, and vacuumizing to the vacuum degree of 2 multiplied by 10-2Pa～3×10-2Pa, and performing vacuum treatment for 60 minutes to deeply remove gas impurities at the welding seam and other parts of the cutter.
And thirdly, heating the cutter substrate to 500-550 ℃, wherein the argon flow is 800-1000 sccm, the ion source voltage is 40-50V, the cutter substrate is biased to 600-800V, and the ion activation treatment time is 60-90 minutes.
Fourthly, heating the cutter base material to 600-650 ℃, keeping the nitrogen flow at 3000-3500 sccm, using an Al/Cr composite target material, specifically 70 at% Al/30 at% Cr composite target material, a target current of 150-180A and a base material bias voltage of 30-36V, adopting a direct current multi-arc method, depositing for 10-15 minutes by PVD, and forming Al with the thickness of 0.2-0.4 mu m on the cutter base materialxCr1-xAnd the x is more than or equal to 0.1 and less than or equal to 0.3.
Fifthly, adjusting the flow rate of nitrogen, gradually reducing the flow rate of nitrogen from 3000-3500 sccm to 0at a speed of 300-600 sccm/min, gradually increasing the flow rate of oxygen from 0 to 3000-3500 sccm at a speed of 300-600 sccm/min, introducing argon, and enabling the flow rate of argon to be 500-1000 sccm; starting high-frequency high-energy pulse magnetic control current, adopting an unbalanced magnetic control combined asymmetric high-frequency pulse method, controlling the magnetic field intensity to be 320-400 gauss, controlling the power of the high-frequency high-energy pulse to be 10-15 kW, controlling the frequency to be 25-50 kHz, controlling the voltage to be 24-40V, controlling the negative pulse width to be 36-40 mu s, controlling the positive pulse width to be 2-4 mu s, controlling the target current to be 150-180A, controlling the substrate bias voltage to be 30-36V, and controlling the PVD deposition time to be 5-8 minutes, wherein Al is subjected to deposition treatmentxCr1-xThe surface of the N layer is 0.1-0.2 μmAlCrN-AlCrON- (AlCr)2O3The intermediate transition layer 22.
Sixthly, oxygen flow of 3000-3500 sccm, argon flow of 500-1000 sccm, power of 10-15 kW, frequency of 25-50 kHz, voltage of 24-40V, negative pulse width of 36-40 mus, positive pulse width of 2-4 mus, target current of 150-180A, substrate bias voltage of 30-36V, PVD deposition time of 10-15 minutes, and formation of 0.2-0.4 mu m Al-Cr-O composite oxide layer 23, wherein the component (Al) isyCr1-y)2O3Wherein y is more than or equal to 0.1 and less than or equal to 0.3.
And seventhly, repeating the fourth step to the sixth step until the thickness of the composite coating 2 on the base material reaches 1.5-6 microns.
By adopting a method of non-equilibrium magnetic control multi-arc (NBMS) and asymmetric high-frequency pulse, the non-equilibrium magnetic field restrains metal ions bombarded by plasma on the target material, avoids the formation of liquid drops, so that the coating deposited on the surface of the workpiece has fine grains and high tool surface finish, as shown in figure 3, FIG. 3(a) is an image of the surface of a coated workpiece obtained by a prior art DC multi-arc process under a magnification of 200 times, FIG. 3(b) is an image of the surface of a coated workpiece obtained by a prior art DC multi-arc process under a magnification of 5000 times, FIG. 3(c) is an image of the surface of the coated workpiece obtained by the magnetron sputtering method of the present invention under a magnification of 5000 times, by comparing the images of FIG. 3(b) and FIG. 3(c), the surface of the coated workpiece obtained by the method of the invention is more smooth than that of the coated workpiece obtained by the comparison method. Meanwhile, the friction and the heat effect between the cutter and the processed material can be effectively reduced, and the temperature of the aluminum oxide coating cutter is 250-400 ℃ lower than that of the cutter without the coating or coated with the composite nitride coating at the high temperature of high-speed dry cutting.
The high-frequency pulse impact is adopted, so that abnormal discharge is eliminated, the target material and the activity are ensured, and the physical vapor deposition process is continuously carried out. The positive pulse width in the asymmetric pulse is narrow, and the ratio of the positive pulse width to the negative pulse width is 1: 9-1: 20, so that the pulse energy loss for PVD sputtering is small, the deposition efficiency is high, and the film layer bonding force is strong.
Table 1 below is a performance evaluation of the major coating types, in terms of coating structure and composition:
table 1: evaluation of Primary coating type Properties
Figure BDA0002654008660000071
Figure BDA0002654008660000081
As can be seen from Table 1, Al2O3The properties in terms of chemical stability, oxidation resistance and high temperature hardness are all optimal in the main coating types. Introduction of the invention and Al2O3The compound nitride gradient combination layer with a similar structure promotes the binding force between the oxide layer and the nitride layer, and ensures the resistance of the high-temperature resistant functional film layer to high-temperature physical abrasion and chemical abrasion.
The technical effect of the cubic boron nitride (CBN/PCBN) tool surface deposition composite coating 2 is illustrated by the following specific application examples:
example (b):
cutter material: coated PCBN blade (65% CBN, 35% TiN as binder)
Processing a workpiece: the high-frequency induction quenching S45C shaft sleeve has the hardness of HRC 56-60 and the depth of a quenching layer of 1.2-2 mm
Cutting speed: 300 to 350m/min
Feeding amount: 0.05mm/rev
Cutting depth: 0.2mm
Comparing the cutter: uncoated PCBN blade and PCBN blade coated with Ti/Al composite nitride coating
Specific results are shown in table 1:
table 1:
Figure BDA0002654008660000082
the above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. A composite coating deposited on the surface of a cubic boron nitride cutter is characterized in that: the composite coating comprises a plurality of sub-composite coatings which are sequentially deposited from the side of the cutter substrate to the outer side, and each sub-composite coating at least comprises an Al-Cr-N layer, a middle transition layer and an Al-Cr-O composite oxide layer which are sequentially deposited from the side of the cutter substrate to the outer side; the Al-Cr-N layer is AlxCr1-xN layer, wherein x is more than or equal to 0.1 and less than or equal to 0.3, and the intermediate transition layer is AlCrN-AlCrON- (AlCr)2O3A transition layer; the Al-Cr-O composite oxide layer is (Al)yCr1-y)2O3Layer, wherein y is more than or equal to 0.1 and less than or equal to 0.3.
2. The composite coating deposited on the surface of a cubic boron nitride tool according to claim 1, wherein: the thickness of the Al-Cr-N layer is 0.2-0.4 mu m, the thickness of the intermediate transition layer is 0.1-0.2 mu m, and the thickness of the Al-Cr-O composite oxide layer is 0.2-0.4 mu m.
3. The composite coating deposited on the surface of a cubic boron nitride tool according to claim 1, wherein: the thickness of the composite coating is 1.5-6 mu m.
4. A method for depositing the composite coating of any one of claims 1 to 3 on the surface of a cubic boron nitride tool by physical vapor deposition, comprising the steps of:
firstly, cleaning and removing water-based and/or hydrocarbon-based pollutants on the surface of a cutter base material;
secondly, heating, vacuumizing and removing gas impurities at the welding seam part of the cutter;
thirdly, plasma etching is carried out, and the tool base material is subjected to activation treatment;
fourthly, heating, introducing nitrogen, using Al/Cr composite target material, adopting a direct current multi-arc method to deposit and form Al on the cutter base materialxCr1-xN layers;
and step five, gradually reducing the nitrogen flow to 0, simultaneously gradually increasing the oxygen flow from 0, introducing argon, starting a high-frequency high-energy pulse magnetic control power supply, adopting an unbalanced magnetic control and asymmetric high-frequency pulse method, wherein the ratio of the positive pulse width to the negative pulse width of the asymmetric high-frequency pulse is 1: 9-1: 20, and adding Al in the Al alloyxCr1-xThe surface of the N layer forms AlCrN-AlCrON- (AlCr)2O3The intermediate transition layer of (3);
sixthly, continuously introducing oxygen, continuously adopting a non-equilibrium magnetic control combined asymmetric high-frequency pulse method to form (Al) on the surface of the intermediate transition layeryCr1-y)2O3A layer;
and seventhly, repeating the fourth step to the sixth step until the thickness of the composite coating on the cutter base material reaches the preset thickness.
5. The method for depositing the composite coating on the surface of the cubic boron nitride cutter by adopting the physical vapor deposition method according to claim 4, wherein the method comprises the following steps: the fourth step is specifically as follows: heating the cutter base material to 600-650 ℃, keeping the nitrogen flow at 3000-3500 sccm, adopting a 70 at% Al/30 at% Cr composite target material as the Al/Cr composite target material, keeping the target current at 150-180A, and keeping the base material biased at 30-36V to form Al on the cutter base materialxCr1-xAnd N layers.
6. The method for depositing the composite coating on the surface of the cubic boron nitride cutter by adopting the physical vapor deposition method according to claim 5, wherein the method comprises the following steps: the fifth step is specifically as follows: the nitrogen flow is adjusted to be gradually reduced to 0 from 3000-3500 sccm, the oxygen flow is gradually increased to 3000-3500 sccm from 0, the argon flow is 500-1000 sccm, the magnetic control magnetic field intensity is 320-400 gauss, the power of high-frequency high-energy pulse is 10-15 kW, the frequency is 25-50 kHZ, the voltage is 24-40V, the negative pulse width is 36-40 mus, the positive pulse width is 2-4 mus, the target current is 150-180A, the base material bias voltage is 30-36V, and Al is addedxCr1-xN-layer tableFace forming AlCrN-AlCrON- (AlCr)2O3The intermediate transition layer of (3).
7. The method for depositing the composite coating on the surface of the cubic boron nitride cutter by adopting the physical vapor deposition method according to claim 4, wherein the method comprises the following steps: the sixth step is specifically as follows: maintaining oxygen flow of 3000-3500 sccm, argon flow of 500-1000 sccm, power of high-frequency high-energy pulse of 10-15 kW, frequency of 25-50 kHz, voltage of 24-40V, negative pulse width of 36-40 mus, positive pulse width of 2-4 mus, target current of 150-180A, substrate bias voltage of 30-36V, forming a surface layer of an intermediate transition layer (Al isyCr1-y)2O3And (3) a layer.
8. A method for depositing a composite coating on the surface of a cubic boron nitride cutter by using a vacuum coating device is characterized by comprising the following steps: the sub-composite coating comprises an Al-Cr-N layer, a middle transition layer and an Al-Cr-O composite oxide layer which are sequentially deposited from the side of the cutter substrate to the outer side, wherein the middle transition layer is a transition layer from AlCrN to AlCrON to AlCrO, and the sub-composite coating is characterized in that: the sub-composite coating is deposited on the surface of the cubic boron nitride cutter base material by an evaporation source, the evaporation source comprises a first group of evaporation sources operated by a direct-current multi-arc power supply and a second group of evaporation sources operated by a high-frequency high-energy pulse magnetic control power supply, the target materials of the first group of evaporation sources and the second group of evaporation sources are Al/Cr composite target materials, and the evaporated Al and Cr react on the surface of the cutter base material in a nitrogen-containing reaction gas environment to form the Al-Cr-N layer by arc discharge generated by the direct-current multi-arc power supply; the non-equilibrium magnetic control glow discharge and the asymmetric high-frequency pulse generated by the high-frequency high-energy pulse magnetic control power supply react the evaporated Al and Cr in a nitrogen and/or oxygen containing reaction gas environment to form a middle transition layer and an Al-Cr-O composite oxide layer on the surface of the Al-Cr-N layer in sequence.
9. The method for depositing the sub-composite coating on the surface of the cubic boron nitride cutter by using the vacuum coating device according to claim 8, wherein: the Al-Cr-N layer is AlxCr1-xN layer, wherein x is more than or equal to 0.1 and less than or equal to 0.3, and the intermediate transition layer is AlCrN-AlCrON-(AlCr)2O3A transition layer; the Al-Cr-O composite oxide layer is (Al)yCr1-y)2O3Layer, wherein y is more than or equal to 0.1 and less than or equal to 0.3.
10. The method for depositing the sub-composite coating on the surface of the cubic boron nitride cutter by using the vacuum coating device according to claim 8, wherein: the ratio of the positive pulse width to the negative pulse width of the asymmetric high-frequency pulse is 1: 9-1: 20.
CN202010880691.4A 2020-08-27 2020-08-27 Composite coating deposited on surface of cubic boron nitride cutter and deposition method Pending CN111945111A (en)

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Publication number Priority date Publication date Assignee Title
CN114736086A (en) * 2021-01-08 2022-07-12 西安近代化学研究所 Boron powder compound with high combustion performance and preparation method thereof
CN114736086B (en) * 2021-01-08 2023-03-17 西安近代化学研究所 Boron powder compound with high combustion performance and preparation method thereof
CN115011920A (en) * 2021-03-05 2022-09-06 株洲钻石切削刀具股份有限公司 Composite coating cutting tool containing double-layer oxide
CN115011919A (en) * 2021-03-05 2022-09-06 株洲钻石切削刀具股份有限公司 Composite coated cutting tool containing multi-period oxide layer
CN115011920B (en) * 2021-03-05 2023-09-05 株洲钻石切削刀具股份有限公司 Composite coated cutting tool containing double layer oxide
CN115011919B (en) * 2021-03-05 2024-02-13 株洲钻石切削刀具股份有限公司 Composite coated cutting tool containing multiple periodic oxide layers
CN115305441A (en) * 2022-08-25 2022-11-08 株洲钻石切削刀具股份有限公司 Composite coated cutting tool with multiple oxide layer structure
CN115305441B (en) * 2022-08-25 2023-09-05 株洲钻石切削刀具股份有限公司 Composite Coated Cutting Tool with Multiple Oxide Layer Structure

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