CN111235515A - Ni-based-Cr3C2ZrN/ZrCN composite coating and cold punching die repairing method - Google Patents

Ni-based-Cr3C2ZrN/ZrCN composite coating and cold punching die repairing method Download PDF

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CN111235515A
CN111235515A CN202010036529.4A CN202010036529A CN111235515A CN 111235515 A CN111235515 A CN 111235515A CN 202010036529 A CN202010036529 A CN 202010036529A CN 111235515 A CN111235515 A CN 111235515A
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coating
zrcn
zrn
punching die
powder
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王爱平
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Guangzhou Jiapeng Technology Co Ltd
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Guangzhou Jiapeng Technology 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D37/00—Tools as parts of machines covered by this subclass
    • B21D37/01—Selection of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D37/00—Tools as parts of machines covered by this subclass
    • B21D37/10—Die sets; Pillar guides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0084—Producing gradient compositions
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0664—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
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Abstract

The invention discloses a Ni-based-Cr3C2a/ZrN/ZrCN composite coating comprising metalA substrate, Ni-based-Cr sequentially deposited on the metal substrate3C2The ZrN gradient coating and the ZrCN gradient coating are formed; the Ni-based-Cr3C2The composite coating is formed by spraying Ni-based alloy powder and Cr3C2-preparing NiCr powder, wherein the ZrN gradient coating and the ZrCN gradient coating are prepared by an ion source assisted non-equilibrium magnetron sputtering technology. The composite coating is applied to repair of a stamping die and a specific repair method, and the overall comprehensive performance of the bonding force, hardness, wear resistance and impact resistance of the repair layer of the stamping die is improved; greatly improving the service life of the stamping die and effectively reducing the production cost.

Description

Ni-based-Cr3C2ZrN/ZrCN composite coating and cold punching die repairing method
Technical Field
The invention relates to a composite coating and a preparation method thereof, in particular to Ni-based-Cr3C2A method for repairing a/Zr/ZrCN composite coating and a cold punching die.
Background
The cold stamping die is required to bear loads such as impact, vibration, friction, high pressure, stretching, bending and the like, and even works at a higher temperature (such as cold extrusion), so that the working condition is complex, and phenomena such as abrasion, fatigue, fracture, deformation and the like are easy to occur. One of the main failure reasons of the cold stamping die is wear failure, which causes unqualified stamping products and severe die scrap, increases production cost and causes economic loss. How to repair the failed stamping die and to achieve remanufacturing of the failed stamping die is the direction of research in the prior art. The common methods include insert bonding, build-up welding, thermal spraying, laser cladding and the like.
Chinese patent CN103911612A discloses a laser repair process for a Cr12MoV cold stamping die taking cobalt-based tungsten carbide as a cladding alloy, which comprises the following steps: 1) cleaning the surface defects of the cold stamping die, and removing surface grinding marks, oil stains and microcracks; 2) adopting Fe316 alloy powder as a priming layer, and carrying out laser priming cladding; 3) adopting Co06+ WC alloy powder as a covering layer, and after the mold is cooled to 300-600 ℃, cladding the covering layer by laser; 4) and machining the surface of the cladding layer. Chinese patent CN106825264A discloses an insert manufacturing method for hot stamping die, comprising the following steps: 1) carrying out rough machining and quenching and tempering on common forged steel or common forging die steel serving as a base material to obtain the basic shape of the insert and reserving a certain allowance; 2) cutting the working surface of the insert by 5-10 mm in the depth direction; 3) welding the high-temperature-resistant and wear-resistant welding core on the working surface of the insert in a surfacing mode to form an additive manufacturing layer, wherein the thickness of the additive manufacturing layer is 1-12 mm; 4) carrying out finish machining on the insert to obtain the insert meeting the use size precision requirement; 5) and carrying out integral quenching on the insert so as to obtain the final insert for the hot stamping die. Chinese patent CN102234754A discloses a repair method for a large-size automobile panel cold stamping die, which is based on reactionAccording to the spraying principle, Mo is prepared on the molded surface of the die to be repaired by an oxyacetylene flame spraying method, a plasma spraying method or a supersonic flame spraying method2FeB2The method comprises the following steps of (1) early treatment, namely a) degreasing and oil removal, b) rust removal, namely rust removal, on a stamping die of a stamping machine, c) phosphating, d) sand blasting, 2) spraying, namely spraying Ni60B-CBN material by using plasma spraying equipment to form a coating, and 3) later treatment, namely polishing by using sand paper.
Although the failed stamping die is repaired in the prior art, a good repairing effect is achieved. However, much research is still needed to further improve the bonding strength, wear resistance, hardness and impact resistance of the repair layer. However, the performance of the coating is greatly related to the composition of the powder, the preparation method and the process parameters, and how to screen out the composition of the powder from a large number of influencing factors and select a proper preparation method and set the process parameters is more creative.
Disclosure of Invention
One object of the present invention is to provide a Ni-based-Cr alloy3C2the/Zr/ZrCN composite coating is used for improving the overall comprehensive performance of the binding force, the hardness, the wear resistance and the impact resistance of the repairing layer of the stamping die. The following technical scheme is adopted: Ni-based-Cr3C2the/ZrN/ZrCN composite coating is characterized by comprising a metal substrate and Ni-based-Cr layers sequentially deposited on the metal substrate3C2The coating comprises a coating, a ZrN gradient coating and a ZrCN gradient coating; the Ni-based-Cr3C2The composite coating is formed by spraying Ni-based alloy powder and Cr through supersonic flame3C2-NiCr powder preparation, said ZrN graded coating and ZrCN graded coating passing throughPreparing an ion source assisted unbalanced magnetron sputtering technology; wherein the Zr content in the ZrN gradient coating gradually increases towards the direction far away from the substrate, and the Zr content in the ZrCN gradient coating gradually decreases towards the direction far away from the substrate.
Further, the metal substrate is Cr12Mo1V1 steel, 45 steel, W18Cr4V steel, or W6Mo5Cr4V2 steel.
Further, the Ni-based alloy powder comprises the following components in percentage by weight: 0.5, Cr: 8.4, B: 0.5, Fe: 1.2, Co: 1.5, Ce: 0.02, Ni balance or C: 0.7, Cr: 9.6, B: 0.8, Fe: 0.8, Co: 2.1, Ce: 0.03 and the balance of Ni.
Further, the Cr is3C2-NiCr powder is Cr3C2-20wt.% NiCr or Cr3C2-25wt.% NiCr powder.
Further, the Ni-based-Cr3C2The thickness of the coating is 120-; the thickness of the ZrN gradual change coating is 15-25 μm; the thickness of the ZrCN gradient coating is 15-25 μm.
Another object of the present invention is to provide a method for repairing a cold punching die, which is characterized in that the Ni-based-Cr is used3C2the/ZrN/ZrCN composite coating comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing the powder according to the weight percentage of 4:1-8:1, placing the mixture in a planetary ball mill to ball mill for 1.0-1.5h under the protection of argon, drying and screening the ball milled powder to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 3 to 6 μm.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled to be 180-200 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 30-40sccm, oxygen flow: 200 ℃ C., 250sccm, powder deliveryArgon flow: 25-35sccm, a powder feeding rate of 20-40g/min, a spraying distance of 120-: 70-80 DEG, obtaining Ni-based-Cr with the thickness of 120-3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) Placing the cold punching die polished in the step (3) on a rotating sample rack of an ion source auxiliary non-equilibrium magnetron sputtering device, and vacuumizing a vacuum cavity to 2-4 multiplied by 10 by adopting two oppositely arranged zirconium targets-3Pa, preheating the cold punching die to 200-250 ℃ through a heating element in the sample frame, and setting the sputtering technological parameters: the rotation speed of the sample holder is 15-25r/min, the Ar flow rate is 200-2The flow rate is 35-45sccm, the working pressure is 0.3-0.5Pa, the substrate negative bias is 200V, the zirconium target current is 40-60A, and the sputtering time is 300-600 s. After the sputtering process is started, other parameters are kept unchanged, the current of the zirconium target is linearly increased to the sputtering completion through a control program, and the current is controlled to be in the Ni base-Cr range3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 15-25 μm; introducing 40-60sccm methane, keeping other parameters unchanged, and linearly reducing the current of the zirconium target to the completion of sputtering by a control program to form Ni-based-Cr3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 15-25 μm; finally obtaining Ni-based-Cr3C2the/ZrN/ZrCN composite coating.
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
Furthermore, the cold punching die is made of Cr12Mo1V1 steel, 45 steel, W18Cr4V steel or W6Mo5Cr4V2 steel.
Further, the process conditions of the sand blasting treatment in the step (2) are as follows: sand blasting and grinding: 30-50 mesh brown corundum, sand blasting distance: 80-100mm, blasting angle: 70-110 °, compressed air pressure: 0.2-0.6 MPa.
Further, the step (5) further comprises the step of preheating the Ni-based-Cr3C2Carrying out ion bombardment treatment on the coating; the sputtering parameters are as follows: the rotation speed of the sample holder is 10-20r/min, the Ar flow rate is 120-150ccm, the working pressure is 0.2-0.3Pa, the negative bias of the substrate is 150-200V, and the sputtering time is 60-90 s.
Further, the ion source is a hall ion source.
Further, the linear increase of the target current of zirconium is specifically: i ist＝I0+ (0.02-0.03) x t; the linear reduction of the current of the zirconium target is specifically It' -I. ' - (0.01-0.02). times.t. Wherein t is 300-600. I ist、It' is the current of the zirconium target at the sputtering time t seconds, I0The target current was set to 40 to 60A, I when the sputtering time t was 0. ' the current of the zirconium target corresponding to the sputtering time for completing the ZrN gradual change coating.
Another object of the present invention is to provide a cold punching die, which is characterized by comprising the Ni-based-Cr3C2the/ZrN/ZrCN composite coating is used as a repairing layer.
The cold punching die is preheated before spraying, so that Ni base-Cr is reduced3C2The temperature difference between the coating and the cold punching die can reduce the thermal stress; on the other hand, the method is beneficial to the surface activation of the cold punching die and the increase of the temperature of the sprayed powder when contacting with the surface, thereby promoting the Ni-based-Cr3C2And the bonding of the coating increases the bonding strength.
The rotation of the cold punching die on the sample frame is controlled in the deposition process of the gradual change coating, so that the coating deposited on the cold punching die is uniform; by applying negative bias to the sample holder, the cold punching die on the sample holder is in a negative potential state, so that positive ions can bombard the surface of the coating, and Ni-based-Cr with excellent compactness is obtained3C2And (4) coating.
Compared with the prior art, the invention has the technical effects that:
(1) the Co-based-WC/ZrN/ZrCN composite coating is prepared by adopting a supersonic flame spraying method and an ion-assisted unbalanced magnetron sputtering technology, has low friction coefficient, wear resistance, hardness and impact resistance, and greatly prolongs the service life of a stamping die.
(2) In the spraying process, the molten spraying powder impacts the surface of the die, and the exothermic reaction is continuously maintained, so that the surface reaches a molten state to form metallurgical bonding, and the bonding force between the die and the Co-based-WC coating is improved.
(3) The ZrN gradient coating and the ZrCN gradient coating are adopted, so that the overall residual stress of the composite coating is reduced, and the tendency of crack generation of a repairing layer is avoided.
(4) The composite coating prepared by the invention is uniform and compact, and has no obvious cracks and air holes.
Drawings
FIG. 1 shows Ni-based-Cr prepared in example 1 and comparative example 13C2a/ZrN/ZrCN composite coating scanning electron microscope image.
FIG. 2 shows Ni-based-Cr prepared in example 1 and comparative example 13C2The friction curve of the/ZrN/ZrCN composite coating.
Detailed Description
The repairing method of the present invention and the composite coating layer obtained thereby will be specifically described below with reference to examples, comparative examples and drawings.
Example 1
A method for repairing a cold punching die comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing NiCr powder according to the weight percentage of 4:1, placing the mixture in a planetary ball mill to ball mill for 1.0h under the protection of argon, drying and screening the ball-milled powder to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder. The Ni-based alloy powder comprises the following components in percentage by weight: 0.5, Cr: 8.4, B: 0.5, Fe: 1.2, Co: 1.5, Ce: 0.02, the balance of Ni; the Cr is3C2-NiCr powder is Cr3C2-20wt.% NiCr powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 4 μm. The cold punching die is made of W18Cr4V steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 40 mesh brown corundum, sand blasting distance: 90mm, blasting angle: 70 °, compressed air pressure: 0.3 MPa.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled at 200 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 40sccm, oxygen flow: 250sccm, flow of powder feeding argon: 30sccm, powder feeding rate of 25g/min, spraying distance of 150mm, and spraying angle: 80 DEG, obtaining Ni-based-Cr with the thickness of 180 mu m3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) Placing the cold punching die polished in the step (3) on a rotating sample rack of an ion source auxiliary non-equilibrium magnetron sputtering device, and vacuumizing a vacuum cavity to 3 multiplied by 10 by adopting two oppositely arranged zirconium targets-3Pa, preheating the cold punching die to 200 ℃ by a heating element in the sample holder, and carrying out Ni-based-Cr annealing3C2Carrying out ion bombardment treatment on the coating; the sputtering parameters are as follows: the rotation speed of the sample holder was 10r/min, the Ar flow rate was 120ccm, the working pressure was 0.22Pa, the negative bias voltage of the substrate was 150, and the sputtering time was 90 s. Setting sputtering technological parameters: the rotating speed of the sample holder is 20r/min, the Ar flow is 250sccm and N2The flow rate is 40sccm, the working pressure is 0.4Pa, the substrate negative bias is 150V, the Hall ion source current is 3A, the zirconium target current is 40A, and the sputtering time is 500 s. After the sputtering process is started, other parameters are kept unchanged, the current of the zirconium target is linearly increased to the sputtering completion through a control program, and the current is controlled to be in the Ni base-Cr range3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 22 mu m; introducing 40sccm methane, keeping other parameters unchanged, and linearly reducing the current of the zirconium target to the completion of sputtering by a control program to obtain Ni-based-Cr3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 16 mu m; finally obtaining Ni-based-Cr3C2the/ZrC/ZrCN composite coating. The linear increase of the zirconium target current is specifically as follows: i ist40+0.03 × t; zirconium target electrodeReduced flow linearity, in particular It’＝45-0.01×t。
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
Comparative example 1
A method for repairing a cold punching die comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing NiCr powder according to the weight percentage of 4:1, placing the mixture in a planetary ball mill to ball mill for 1.0h under the protection of argon, drying and screening the ball-milled powder to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder. The Ni-based alloy powder comprises the following components in percentage by weight: 0.5, Cr: 8.4, B: 0.5, Fe: 1.2, Co: 1.5, Ce: 0.02, the balance of Ni; the Cr is3C2-NiCr powder is Cr3C2-20wt.% NiCr powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 4 μm. The cold punching die is made of W18Cr4V steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 40 mesh brown corundum, sand blasting distance: 90mm, blasting angle: 70 °, compressed air pressure: 0.3 MPa.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled at 200 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 40sccm, oxygen flow: 250sccm, flow of powder feeding argon: 30sccm, powder feeding rate of 25g/min, spraying distance of 150mm, and spraying angle: 80 DEG, obtaining Ni-based-Cr with the thickness of 180 mu m3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) Placing the cold punching die polished in the step (3) in an ion source to assist the unbalanced magnetron sputteringOn a rotary sample rack of the injection equipment, two oppositely arranged zirconium targets are adopted to vacuumize a vacuum cavity to 3 multiplied by 10-3Pa, preheating the cold punching die to 200 ℃ by a heating element in the sample holder, and carrying out Ni-based-Cr annealing3C2Carrying out ion bombardment treatment on the coating; the sputtering parameters are as follows: the rotation speed of the sample holder was 10r/min, the Ar flow rate was 120ccm, the working pressure was 0.22Pa, the negative bias voltage of the substrate was 150, and the sputtering time was 90 s. Setting sputtering technological parameters: the rotating speed of the sample holder is 20r/min, the Ar flow is 250sccm and N2The flow rate is 40sccm, the working pressure is 0.4Pa, the substrate negative bias is 150V, the Hall ion source current is 3A, the zirconium target current is 40A, and the sputtering time is 500 s. After the sputtering process is started, the parameters are kept unchanged, and the sputtering process is carried out on Ni base-Cr3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 20 mu m; introducing 40sccm methane, keeping the parameters unchanged, and introducing Ni-based-Cr3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 21 mu m; finally obtaining Ni-based-Cr3C2the/ZrN/ZrCN composite coating.
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
Example 1 differs from comparative example 1 in that the zirconium target current during sputtering in comparative example 1 remains unchanged.
Example 2
A method for repairing a cold punching die comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing NiCr powder according to the weight percentage of 8:1, placing the mixture in a planetary ball mill, carrying out ball milling for 1.5.0h under the argon protective atmosphere, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder. The Ni-based alloy powder comprises the following components in percentage by weight: 0.7, Cr: 9.6, B: 0.8, Fe: 0.8, Co: 2.1, Ce: 0.03 and the balance of Ni; the Cr is3C2-NiCr powder is Cr3C2-25wt.% NiCr powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 6 μm. The cold punching die is made of W6Mo5Cr4V2 steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 30 mesh brown corundum, sand blasting distance: 100mm, blasting angle: 80 °, compressed air pressure: 0.6 MPa.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled at 180 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 30sccm, oxygen flow: 200sccm, flow of powder feeding argon: 35sccm, a powder feeding rate of 20g/min, a spraying distance of 120mm, and a spraying angle: 80 DEG, obtaining Ni-based-Cr with the thickness of 150 mu m3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) Placing the cold punching die polished in the step (3) on a rotating sample rack of an ion source auxiliary non-equilibrium magnetron sputtering device, and vacuumizing a vacuum cavity to 3.5 multiplied by 10 by adopting two oppositely arranged zirconium targets-3Pa, preheating the cold punching die to 220 ℃ through a heating element in the sample frame, and setting sputtering technological parameters: the rotating speed of the sample holder is 25r/min, the Ar flow is 200sccm and N2The flow rate is 35sccm, the working pressure is 0.3Pa, the substrate negative bias is 180V, the Hall ion source current is 5A, the zirconium target current is 60A, and the sputtering time is 600 s. After the sputtering process is started, other parameters are kept unchanged, the current of the zirconium target is linearly increased to the sputtering completion through a control program, and the current is controlled to be in the Ni base-Cr range3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 21 mu m; 60sccm methane is introduced, other parameters are kept unchanged, the current of the zirconium target is linearly reduced to the completion of sputtering by a control program, and the target is subjected to Ni-based-Cr sputtering3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 24 mu m; finally obtaining Ni-based-Cr3C2the/ZrN/ZrCN composite coating. Linear increase of zirconium target currentThe method specifically comprises the following steps: i ist60+0.03 × t; the linear reduction of the current of the zirconium target is specifically It’＝78-0.02×t。
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
Comparative example 2
A method for repairing a cold punching die comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing NiCr powder according to the weight percentage of 8:1, placing the mixture in a planetary ball mill, carrying out ball milling for 1.5.0h under the argon protective atmosphere, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder. The Ni-based alloy powder comprises the following components in percentage by weight: 0.7, Cr: 9.6, B: 0.8, Fe: 0.8, Co: 2.1, Ce: 0.03 and the balance of Ni; the Cr is3C2-NiCr powder is Cr3C2-25wt.% NiCr powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 6 μm. The cold punching die is made of W6Mo5Cr4V2 steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 30 mesh brown corundum, sand blasting distance: 100mm, blasting angle: 80 °, compressed air pressure: 0.6 MPa.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled at 180 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 30sccm, oxygen flow: 200sccm, flow of powder feeding argon: 35sccm, a powder feeding rate of 20g/min, a spraying distance of 120mm, and a spraying angle: 80 DEG, obtaining Ni-based-Cr with the thickness of 150 mu m3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) After being polished in the step (3)The cold punching die is arranged on a rotating sample frame of the ion source auxiliary non-equilibrium magnetron sputtering equipment, two oppositely arranged zirconium targets are adopted, and a vacuum cavity is vacuumized to 3.5 multiplied by 10-3Pa, preheating the cold punching die to 220 ℃ through a heating element in the sample frame, and setting sputtering technological parameters: the rotating speed of the sample holder is 25r/min, the Ar flow is 200sccm and N2The flow rate is 35sccm, the working pressure is 0.3Pa, the substrate negative bias is 180V, the Hall ion source current is 5A, the zirconium target current is 60A, and the sputtering time is 600 s. After the sputtering process is started, the parameters are kept unchanged, and the sputtering process is carried out on Ni base-Cr3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 17 mu m; 60sccm methane is introduced, parameters are kept unchanged, and Ni base-Cr is added3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 20 mu m; finally obtaining Ni-based-Cr3C2the/ZrC/ZrCN composite coating.
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
Example 2 differs from comparative example 2 in that the zirconium target current during sputtering in comparative example 2 remains unchanged.
The technical scheme and the effect of the invention are explained in detail below mainly aiming at the performance characterization of the composite coatings prepared in example 1 and comparative example 1.
FIG. 1(a) shows Ni-based-Cr prepared in example 13C2Scanning electron micrograph of/ZrN/ZrCN composite coating, FIG. 1(b) is Ni-based-Cr prepared in comparative example 13C2a/ZrN/ZrCN composite coating scanning electron microscope image. As can be seen from the figure, the coatings prepared by the two methods have compact structures and relatively even roughness, but the composite coating prepared by the comparative example has a plurality of cracks, but the composite coating prepared by the embodiment has no defects such as cracks and other pores, and the like, so that the excellent wear resistance and the service life of the coating in a wear-resistant environment are ensured.
The friction and wear test adopts an MMW-1 type vertical universal wear test machine. The experimental conditions are as follows: dry friction, room temperature, friction pair using Si with diameter of 5mm3N4Ceramic spheres, a friction speed of 150r/min and a load of 80N. And measuring the weight loss before and after abrasion by using a high-precision electronic balance, and calculating to obtain the abrasion rate. And obtaining a friction coefficient curve and fitting and calculating data to obtain the friction coefficient.
Fig. 2(a) is a friction curve of example 1, and fig. 2(b) is a friction curve of comparative example 1. From the friction curve analysis, the friction coefficients of the composite coatings prepared in the examples and comparative examples are relatively stable in the friction test, however, the friction coefficient of the composite coating prepared in the example 1 is lower, and the friction coefficient values obtained by fitting are recorded in the table 1. Through comparison, the repair layer prepared by the invention has a friction coefficient lower than that of the comparative example by 60%. Therefore, the repair layer prepared by the method has better wear resistance and service life under the same experimental conditions.
And (3) testing the bonding strength: the application of the bonding strength of the coating and the substrate in engineering is very important and is one of the key indexes for evaluating the quality of the coating. The Ni-based-Cr of the present invention3C2The bonding strength of the/ZrN/ZrCN composite coating is subjected to a tensile test according to the ASTM C-633-79 standard.
And (3) hardness testing: hardness is an important mechanical property of the coating, and is related to the wear resistance and service life of the coating during operation. The method adopts a metallographic microhardness meter to measure the microhardness (HV) of the repair layer. The microhardness of different areas of the repair layer is different due to the incomplete uniformity, compactness and consistent composition of the repair layer. Therefore, 5 points are selected at four corners and a central area of the coating respectively to measure the microhardness, and then an average value is taken as the average microhardness of the repair layer. Specific average microhardness results are reported in table 1. As can be seen from the results of table 1, the repair layer prepared by the present invention has good wear resistance and lubricity, and the average microhardness is significantly higher than that of comparative example 1.
TABLE 1
Figure BDA0002366216480000101
The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. Ni-based-Cr3C2the/ZrN/ZrCN composite coating is used for improving the overall comprehensive performance of the bonding force, the hardness, the wear resistance and the impact resistance of the repairing layer of the stamping die. The following technical scheme is adopted: Ni-based-Cr3C2the/ZrN/ZrCN composite coating is characterized by comprising a metal substrate and Ni-based-Cr layers sequentially deposited on the metal substrate3C2The coating comprises a coating, a ZrN gradient coating and a ZrCN gradient coating; the Ni-based-Cr3C2The composite coating is formed by spraying Ni-based alloy powder and Cr through supersonic flame3C2-preparing NiCr powder, wherein the ZrN gradient coating and the ZrCN gradient coating are prepared by an ion source assisted non-equilibrium magnetron sputtering technology; wherein the Zr content in the ZrN gradient coating gradually increases towards the direction far away from the substrate, and the Zr content in the ZrCN gradient coating gradually decreases towards the direction far away from the substrate; the metal substrate is Cr12Mo1V1 steel, 45 steel, W18Cr4V steel or W6Mo5Cr4V2 steel.
2. The Ni-based-Cr-alloy according to claim 13C2the/ZrN/ZrCN composite coating is characterized in that the Ni-based alloy powder comprises the following components in percentage by weight: 0.5, Cr: 8.4, B: 0.5, Fe: 1.2, Co: 1.5, Ce: 0.02, Ni balance or C: 0.7, Cr: 9.6, B: 0.8, Fe: 0.8, Co: 2.1, Ce: 0.03 and the balance of Ni.
3. The Ni-based-Cr according to any one of claims 1 to 23C2the/ZrN/ZrCN composite coating is characterized in that the Cr is3C2-NiCr powder is Cr3C2-20wt.% NiCr or Cr3C2-25wt.% NiCr powder.
4. The Ni-based-Cr-alloy according to any one of claims 1 to 33C2the/ZrN/ZrCN composite coating is characterized in that the Ni-based-Cr3C2The thickness of the coating is 120-; the thickness of the ZrN gradual change coating is 15-25 μm; the thickness of the ZrCN gradient coating is 15-25 μm.
5. A method for repairing a cold punching die, characterized in that the Ni-based-Cr alloy of any one of claims 1 to 4 is used3C2the/ZrN/ZrCN composite coating comprises the following steps:
(1) mixing Ni-base alloy powder with Cr3C2Mixing the powder according to the weight percentage of 4:1-8:1, placing the mixture in a planetary ball mill to ball mill for 1.0-1.5h under the protection of argon, drying and screening the ball milled powder to obtain composite powder with the particle size diameter of 40-70 mu m, and sealing and storing the powder.
(2) Polishing the worn part of the stamping die to be repaired, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol, acetone and deionized water, and drying; the mold was subjected to sand blasting to obtain a surface roughness Ra of 3 to 6 μm.
(3) Placing a cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-acetylene flame, wherein the preheating temperature is controlled to be 180-200 ℃; next, adjusting the parameters of the spraying process: acetylene flow rate: 30-40sccm, oxygen flow: 200-250sccm, powder feeding argon flow: 25-35sccm, a powder feeding rate of 20-40g/min, a spraying distance of 120-: 70-80 DEG, obtaining Ni-based-Cr with the thickness of 120-3C2And (4) coating.
(4) For the Ni-based-Cr obtained in the step (3)3C2And (3) polishing the coating, sequentially polishing by adopting 800#, 1000# and 1200# metallographic abrasive paper, cleaning and drying.
(5) Placing the cold punching die polished in the step (3) on a rotating sample rack of ion-assisted unbalanced magnetron sputtering equipment, and vacuumizing a vacuum cavity to 2-4 multiplied by 10 by adopting two oppositely-arranged zirconium targets-3Pa, cold punching die by heating element in sample holderPreheating to 200 ℃ and 250 ℃, setting sputtering process parameters: the rotation speed of the sample holder is 15-25r/min, the Ar flow rate is 200-2The flow rate is 35-45sccm, the working pressure is 0.3-0.5Pa, the substrate negative bias is 150-200V, the ion source current is 3-5A, the zirconium target current is 40-60A, and the sputtering time is 300-600 s. After the sputtering process is started, other parameters are kept unchanged, the current of the zirconium target is linearly increased to the sputtering completion through a control program, and the current is controlled to be in the Ni base-Cr range3C2Depositing a ZrN gradual change coating on the surface of the coating, wherein the thickness of the ZrN gradual change coating is 15-25 μm; introducing 40-60sccm methane, keeping other parameters unchanged, and linearly reducing the current of the zirconium target to the completion of sputtering by a control program to form Ni-based-Cr3C2Depositing a ZrCN gradual change coating on the surface of the coating, wherein the thickness of the ZrCN gradual change coating is 15-25 μm; finally obtaining Ni-based-Cr3C2the/ZrN/ZrCN composite coating.
(6) And (5) grinding and polishing the cold punching die in the step (5), wherein the size of the repaired area after treatment is the same as the original size.
6. The method for repairing a cold punching die according to claim 5, wherein the material of the cold punching die is Cr12Mo1V1 steel, 45 steel, W18Cr4V steel or W6Mo5Cr4V2 steel.
7. A cold-punching die repairing method according to any one of claims 5-6, wherein said sand-blasting treatment of step (2) is carried out under the following process conditions: sand blasting and grinding: 30-50 mesh brown corundum, sand blasting distance: 80-100mm, blasting angle: 70-110 °, compressed air pressure: 0.2-0.6 MPa.
8. A cold-punching die repairing method according to any one of claims 5-7, wherein step (5) further comprises applying Ni-based-Cr after preheating3C2Carrying out ion bombardment treatment on the coating; the sputtering parameters are as follows: the rotation speed of the sample holder is 10-20r/min, the Ar flow rate is 120-150ccm, the working pressure is 0.2-0.3Pa, the negative bias of the substrate is 150-200V, and the sputtering time is 60-90 s.
9. A cold-punching die repairing method according to any one of claims 6-8, wherein the linear increase of the target current of zirconium is specifically: i ist=I0+ (0.02-0.03) x t; the linear reduction of the current of the zirconium target is specifically It ’=I。 ’- (0.01-0.02). times.t. Wherein t is 300-600.
10. A cold-punching die comprising the Ni-based-Cr alloy as set forth in any one of claims 1 to 93C2the/ZrN/ZrCN composite coating is used as a repairing layer.
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Publication number Priority date Publication date Assignee Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115584470A (en) * 2022-10-24 2023-01-10 安徽工业大学 Through Zr/Zr 2 Method for improving corrosion and abrasion resistance of titanium alloy surface by N/ZrN multilayer coating

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