CN111118436A - Co-based-WC/TiN/TiCN composite coating and cold punching die repairing method - Google Patents

Co-based-WC/TiN/TiCN composite coating and cold punching die repairing method Download PDF

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CN111118436A
CN111118436A CN202010036539.8A CN202010036539A CN111118436A CN 111118436 A CN111118436 A CN 111118436A CN 202010036539 A CN202010036539 A CN 202010036539A CN 111118436 A CN111118436 A CN 111118436A
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coating
tin
ticn
powder
punching die
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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
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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

Abstract

The invention discloses a Co-based-WC/TiN/TiCN composite coating, which comprises a metal substrate, a Co-based-WC coating, a TiN gradient coating and a TiCN gradient coating, wherein the Co-based-WC coating, the TiN gradient coating and the TiCN gradient coating are sequentially deposited on the metal substrate; the Co-based-WC composite coating is prepared by spraying Co-based alloy powder and WC powder through supersonic flame, and the TiN gradient coating and the TiCN gradient coating are prepared through an ion-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

Co-based-WC/TiN/TiCN 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 a Co-based-WC/TiN/TiCN composite coating and a cold punching die repairing method.
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 method for repairing a large-size automobile panel cold stamping die, which is based on the reaction spraying principle, and Mo is prepared on the molded surface of the die to be repaired by oxy-acetylene flame spraying, plasma spraying or supersonic flame spraying2FeB2The 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 of the purposes of the invention is to provide a Co-based-WC/TiN/TiCN composite coating to improve the overall comprehensive performance of the bonding force, hardness, wear resistance and impact resistance of a repairing layer of a stamping die. The following technical scheme is adopted: a Co-based-WC/TiN/TiCN composite coating is characterized by comprising a metal substrate, a Co-based-WC coating, a TiN gradient coating and a TiCN gradient coating which are sequentially deposited on the metal substrate; the Co-based-WC composite coating is prepared by spraying Co-based alloy powder and WC-Co powder through supersonic flame, and the TiN gradient coating and the TiCN gradient coating are prepared through an ion source assisted non-equilibrium magnetron sputtering technology; wherein the content of Ti in the TiN gradient coating gradually increases towards the direction far away from the substrate, and the content of Ti in the TiCN 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 Co-based alloy powder comprises the following components in percentage by weight: 0.5, Ni: 2.4, Cr: 27. fe: 1.7, Mn: 0.4, Mo: 1.2, Y: 0.04, balance of Co or C: 1.2, Ni: 2.7, Cr: 33. fe: 3.1, Mn: 0.5, Mo: 0.7, Y: 0.07, and the balance of Co.
Further, the WC-Co powder is WC-12wt.% Co or WC-17 wt.% Co powder.
Further, the thickness of the Co-based-WC coating is 150-250 μm; the thickness of the TiN gradient coating is 20-30 mu m; the thickness of the TiCN gradient coating is 20-30 mu m.
The invention also aims to provide a method for repairing the cold punching die, which is characterized in that the Co-based-WC/TiN/TiCN composite coating is used, and the method comprises the following steps:
(1) mixing Co-based alloy powder and WC-Co powder according to the weight percentage of 3:1-9:1, placing the mixture in a planetary ball mill to ball mill for 1.5-2h under the protection of argon gas, drying and screening the ball-milled powder to obtain composite powder with the particle size diameter of 30-60 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 1 to 5 μm.
(3) Placing the cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-propane flame, wherein the preheating temperature is controlled to be 200-250 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 25-35sccm, oxygen flow: 150-200sccm, powder feeding argon flow: 20-30sccm, powder feeding rate 20-30g/min, spraying distance 150-: 70-80 deg., obtaining a Co-based-WC coating with a thickness of 150-.
(4) And (4) polishing the Co-based-WC coating obtained in the step (3), 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 titanium targets which are oppositely arranged are adopted, and a vacuum cavity is vacuumized to 1-4 multiplied by 10-3Pa, preheating the cold punching die to 150-: the rotation speed of the sample holder is 10-20r/min, the Ar flow is 150-2The flow rate is 40-60sccm, the working pressure is 0.2-0.5Pa, the substrate negative bias is 180-220V, the ion source current is 2-5A, the titanium target current is 30-50A, and the sputtering time is 300-600 s. After the sputtering process is started, keeping other parameters unchanged, linearly increasing the current of a titanium target to the completion of sputtering by a control program, and depositing a TiN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiN gradient coating is 20-30 μm; introducing 40-60sccm methane, keeping other parameters unchanged, linearly reducing the current of the titanium target to the completion of sputtering by a control program, and depositing a TiCN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiCN gradient coating is 20-30 mu m; finally obtaining the Co-based-WC/TiN/TiCN 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) also comprises the step of carrying out ion bombardment treatment on the Co-based-WC coating after preheating; the sputtering parameters are as follows: the rotation speed of the sample holder is 10-20r/min, the Ar flow is 100-150ccm, the working pressure is 0.1-0.3Pa, the negative bias of the substrate is 150-200V, and the sputtering time is 60-120 s.
Further, the ion source is a hall ion source.
Further, the linear increase of the titanium target current is specifically as follows: i ist＝I0+ (0.02-0.03) x t; the linear reduction of the titanium target current is specifically It’＝I。' - (0.01-0.02). times.t. Wherein t is 300-600. I ist、It' isTitanium target current corresponding to sputtering time t seconds, I0Titanium target current 30-50A, I set for sputtering time t equal to 0。' titanium target current corresponding to sputtering time for completing TiN gradient coating.
The invention also aims to provide a cold punching die which is characterized by comprising the Co-based-WC/TiN/TiCN composite coating as a repairing layer.
The cold punching die is preheated before spraying, so that the temperature difference between the Co-based-WC coating and the cold punching die is reduced, and the thermal stress can be reduced; 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 the sprayed powder is contacted with the surface, thereby promoting the combination of the Co-based-WC coating and increasing the combination 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 the Co-based-WC coating with excellent compactness is obtained.
Compared with the prior art, the invention has the technical effects that:
(1) the Co-based-WC/TiN/TiCN composite coating is prepared by adopting a supersonic flame spraying method and an ion source 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 TiN gradient coating and the TiCN gradient coating are adopted, so that the overall residual stress of the composite coating is favorably reduced, and the trend of generating cracks on the repair 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 is a scanning electron microscope image of the Co-based-WC/TiN/TiCN composite coating prepared in example 1 and comparative example 1.
FIG. 2 is a friction curve of the Co-based-WC/TiN/TiCN composite coatings prepared in example 1 and comparative example 1.
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 Co-based alloy powder and WC-Co powder according to a weight percentage of 4:1, placing the mixture in a planetary ball mill to perform ball milling for 2 hours in an argon protective atmosphere, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 30-60 mu m, and sealing and storing the powder. The Co-based alloy powder comprises the following components in percentage by weight: 0.5, Ni: 2.4, Cr: 27. fe: 1.7, Mn: 0.4, Mo: 1.2, Y: 0.04, the balance of Co; the WC-Co powder is WC-12wt.% Co 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 5 μm. The cold punching die is made of Cr12Mo1V1 steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 50 mesh brown corundum, sand blasting distance: 100mm, blasting angle: 80 °, compressed air pressure: 0.4 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-propane flame, wherein the preheating temperature is controlled at 250 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 35sccm, oxygen flow: 200sccm, flow of powder feeding argon: 30sccm, a powder feeding rate of 30g/min, a spraying distance of 200mm, and a spraying angle: 75 deg., a Co-based-WC coating with a thickness of 200 μm was obtained.
(4) And (4) polishing the Co-based-WC coating obtained in the step (3), 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) inOn a rotating sample rack of the ion source auxiliary unbalanced magnetron sputtering equipment, two titanium targets which are oppositely arranged are adopted to vacuumize a vacuum cavity to 4 multiplied by 10-3Pa, preheating a cold punching die to 200 ℃ through a heating element in a sample frame, and carrying out ion bombardment treatment on the Co-based-WC coating: the sputtering parameters are as follows: the rotation speed of the sample holder is 15r/min, the Ar flow is 100ccm, the working pressure is 0.15Pa, the negative bias of the substrate is 150V, and the sputtering time is 60 s. Setting sputtering technological parameters: the rotating speed of the sample holder is 15r/min, the Ar flow is 180sccm, N2The flow rate is 60sccm, the working pressure is 0.5Pa, the negative bias voltage of the substrate is 200V, the current of the Hall ion source is 2A, the current of the titanium target is 50A, and the sputtering time is 600 s. After the sputtering process is started, keeping other parameters unchanged, linearly increasing the current of a titanium target to the completion of sputtering by a control program, and depositing a TiN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiN gradient coating is 25 mu m; introducing 60sccm methane, keeping other parameters unchanged, linearly reducing the current of the titanium target to the completion of sputtering by a control program, and depositing a TiCN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiCN gradient coating is 27 mu m; finally obtaining the Co-based-WC/TiN/TiCN composite coating. The linear increase of the titanium target current is specifically as follows: i ist50+0.03 × t; the linear increase of the titanium target current is specifically It’＝68-0.01×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 Co-based alloy powder and WC-Co powder according to a weight percentage of 4:1, placing the mixture in a planetary ball mill to perform ball milling for 2 hours in an argon protective atmosphere, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 30-60 mu m, and sealing and storing the powder. The Co-based alloy powder comprises the following components in percentage by weight: 0.5, Ni: 2.4, Cr: 27. fe: 1.7, Mn: 0.4, Mo: 1.2, Y: 0.04, the balance of Co; the WC-Co powder is WC-12wt.% Co 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 5 μm. The cold punching die is made of Cr12Mo1V1 steel. The process conditions of the sand blasting treatment are as follows: sand blasting and grinding: 50 mesh brown corundum, sand blasting distance: 100mm, blasting angle: 80 °, compressed air pressure: 0.4 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-propane flame, wherein the preheating temperature is controlled at 250 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 35sccm, oxygen flow: 200sccm, flow of powder feeding argon: 30sccm, a powder feeding rate of 30g/min, a spraying distance of 200mm, and a spraying angle: 75 deg., a Co-based-WC coating with a thickness of 200 μm was obtained.
(4) And (4) polishing the Co-based-WC coating obtained in the step (3), 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 4 multiplied by 10 by adopting two titanium targets which are oppositely arranged-3Pa, preheating a cold punching die to 200 ℃ through a heating element in a sample frame, and carrying out ion bombardment treatment on the Co-based-WC coating: the sputtering parameters are as follows: the rotation speed of the sample holder is 15r/min, the Ar flow is 100ccm, the working pressure is 0.15Pa, the negative bias of the substrate is 150V, and the sputtering time is 60 s. Setting sputtering technological parameters: the rotating speed of the sample holder is 15r/min, the Ar flow is 180sccm, N2The flow rate is 60sccm, the working pressure is 0.5Pa, the negative bias voltage of the substrate is 200V, the current of the Hall ion source is 2A, the current of the titanium target is 50A, and the sputtering time is 600 s. Depositing a TiN coating on the surface of the Co-based-WC coating, wherein the thickness of the gradient coating is 22 mu m; introducing 60sccm methane, keeping other parameters unchanged, and depositing a TiCN coating on the surface of the Co-based-WC coating, wherein the thickness of the TiCN coating is 30 mu m; finally obtaining the Co-based-WC/TiN/TiCN 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 titanium 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 Co-based alloy powder and WC-Co powder according to the weight percentage of 9:1, placing the mixture in a planetary ball mill to perform ball milling for 1.5 hours under the protection of argon gas, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 30-60 mu m, and sealing and storing the powder. The Co-based alloy powder comprises the following components in percentage by weight: 1.2, Ni: 2.7, Cr: 33. fe: 3.1, Mn: 0.5, Mo: 0.7, Y: 0.07, and the balance of Co. The WC-Co powder is WC-17 wt.% Co 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: 90 °, 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-propane flame, wherein the preheating temperature is controlled at 220 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 30sccm, oxygen flow: 150sccm, flow of argon powder feed: 20sccm, powder feeding rate of 20g/min, spraying distance of 150mm, and spraying angle: 75 deg., a Co-based-WC coating with a thickness of 150 μm was obtained.
(4) And (4) polishing the Co-based-WC coating obtained in the step (3), 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 4 multiplied by 10 by adopting two titanium targets which are oppositely arranged-3Pa, preheating the cold punching die to 200 ℃ through a heating element in the sample frame, and setting sputtering technological parameters: sample rackThe rotation speed is 18r/min, the Ar flow rate is 160sccm, N2The flow rate is 50sccm, the working pressure is 0.4Pa, the negative bias of the substrate is 180V, the ion source current is 5A, the titanium target current is 40A, and the sputtering time is 500 s. After the sputtering process is started, keeping other parameters unchanged, linearly increasing the current of a titanium target to the completion of sputtering by a control program, and depositing a TiN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiN gradient coating is 20 mu m; introducing 50sccm methane, keeping other parameters unchanged, linearly reducing the current of the titanium target to the completion of sputtering by a control program, and depositing a TiCN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiCN gradient coating is 22 mu m; finally obtaining the Co-based-WC/TiN/TiCN composite coating. The linear increase of the titanium target current is specifically as follows: i ist40+0.02 × t; the linear increase of the titanium target current is specifically It’＝48-0.01×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 2
A method for repairing a cold punching die comprises the following steps:
(1) mixing Co-based alloy powder and WC-Co powder according to the weight percentage of 9:1, placing the mixture in a planetary ball mill to perform ball milling for 1.5 hours under the protection of argon gas, drying and screening the powder after ball milling to obtain composite powder with the particle size diameter of 30-60 mu m, and sealing and storing the powder. The Co-based alloy powder comprises the following components in percentage by weight: 1.2, Ni: 2.7, Cr: 33. fe: 3.1, Mn: 0.5, Mo: 0.7, Y: 0.07, and the balance of Co. The WC-Co powder is WC-17 wt.% Co 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: 90 °, 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-propane flame, wherein the preheating temperature is controlled at 220 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 30sccm, oxygen flow: 150sccm, flow of argon powder feed: 20sccm, powder feeding rate of 20g/min, spraying distance of 150mm, and spraying angle: 75 deg., a Co-based-WC coating with a thickness of 150 μm was obtained.
(4) And (4) polishing the Co-based-WC coating obtained in the step (3), 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 4 multiplied by 10 by adopting two titanium targets which are oppositely arranged-3Pa, preheating the cold punching die to 200 ℃ through a heating element in the sample frame, and setting sputtering technological parameters: the rotating speed of the sample holder is 18r/min, the Ar flow is 160sccm and N2The flow is 50sccm, the working pressure is 0.4Pa, the substrate negative bias is 180V, the Hall ion source current is 5A, the titanium target current is 40A, and the sputtering time is 500 s. Depositing a TiN coating on the surface of the Co-based-WC coating, wherein the thickness of the gradient coating is 18 mu m; 50sccm methane is introduced, other parameters are kept unchanged, and a TiCN coating is deposited on the surface of the Co-based-WC coating, wherein the thickness of the TiCN coating is 27 mu m; finally obtaining the Co-based-WC/TiN/TiCN 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 titanium target current during sputtering in comparative example 1 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) is a scanning electron microscope image of the Co-based-WC/TiN/TiCN composite coating prepared in example 1, and FIG. 1(b) is a scanning electron microscope image of the Co-based-WC/TiN/TiCN composite coating prepared in comparative example 1. As can be seen from the figure, the coatings prepared by the two methods have compact structures and relatively even roughness, and have no defects such as cracks, other air holes and the like, so that the excellent wear resistance and the service life of the coatings 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, a load of 80N and a friction time of 1200 s. 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 coatings prepared in the examples exhibited a smoother average coefficient of friction in the friction test than the comparative examples, and example 1 had a lower coefficient of friction, and the values of the coefficients of friction obtained by the fitting are reported in table 1. By comparison, the repair layer prepared by the invention has a friction coefficient lower than that of the comparative example 56%. 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 bonding strength of the Co-based-WC/TiN/TiCN composite coating of the invention 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.
And (3) impact resistance test: the coatings of example 1 and comparative example 1 were subjected to an impact test using a ball drop impact tester. The diameter of the steel ball for testing is 11.5mm, and the ball falling height is 80 cm. And recording the number of the falling steel balls (namely the impact times) when the coating cracks and peels off. The impact resistance test was repeated 5 times, and the average number of times (rounded off after decimal) was taken, and the results are reported in table 1. According to experimental results, the repair layer prepared by the method has good impact resistance, and the impact resistance is improved by 21.5%.
TABLE 1
Figure BDA0002366223160000101
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. A Co-based-WC/TiN/TiCN composite coating is used for improving the overall comprehensive performance of the binding force, hardness, wear resistance and impact resistance of a repairing layer of a stamping die. The following technical scheme is adopted: a Co-based-WC/TiN/TiCN composite coating is characterized by comprising a metal substrate, a Co-based-WC coating, a TiN gradient coating and a TiCN gradient coating which are sequentially deposited on the metal substrate; the Co-based-WC composite coating is prepared by spraying Co-based alloy powder and WC-Co powder through supersonic flame, and the TiN gradient coating and the TiCN gradient coating are prepared through an ion source assisted non-equilibrium magnetron sputtering technology; wherein the content of Ti in the TiN gradient coating gradually increases towards the direction far away from the substrate, and the content of Ti in the TiCN 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 Co-based-WC/TiN/TiCN composite coating of claim 1, wherein the composition of the Co-based alloy powder is, in weight percent, C: 0.5, Ni: 2.4, Cr: 27. fe: 1.7, Mn: 0.4, Mo: 1.2, Y: 0.04, balance of Co or C: 1.2, Ni: 2.7, Cr: 33. fe: 3.1, Mn: 0.5, Mo: 0.7, Y: 0.07, and the balance of Co.
3. A Co-based-WC/TiN/TiCN composite coating according to any of claims 1-2, characterized in that the WC-Co powder is WC-12wt.% Co or WC-1712wt.% Co powder.
4. The Co-based-WC/TiN/TiCN composite coating according to any of the claims 1-3, wherein the thickness of the Co-based-WC coating is 150-; the thickness of the TiN gradient coating is 20-30 mu m; the thickness of the TiCN gradient coating is 20-30 mu m.
5. A method for repairing a cold-punched mold, characterized in that a Co-based-WC/TiN/TiCN composite coating according to any one of claims 1 to 4 is used, comprising the steps of:
(1) mixing Co-based alloy powder and WC-Co powder according to the weight percentage of 3:1-9:1, placing the mixture in a planetary ball mill to perform ball milling for 1.5-2 hours under the protection of argon gas, drying and screening the ball-milled powder to obtain composite powder with the particle size diameter of 30-60 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; carrying out sand blasting treatment on the mould to obtain the surface roughness Ra of 1-5 mu m;
(3) placing the cold punching die on a sample rack in supersonic flame spraying equipment, and preheating the cold punching die by using oxygen-propane flame, wherein the preheating temperature is controlled to be 200-250 ℃; next, adjusting the parameters of the spraying process: flow rate of propane: 25-35sccm, oxygen flow: 150-200sccm, powder feeding argon flow: 20-30sccm, powder feeding rate 20-30g/min, spraying distance 150-: 70-80 degrees to obtain a Co-based-WC coating with the thickness of 150-;
(4) polishing the Co-based-WC coating obtained in the step (3), sequentially polishing with 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 1-4 multiplied by 10 by adopting two titanium targets which are oppositely arranged-3Pa, preheating the cold punching die to 150-: the rotation speed of the sample holder is 10-20r/min, the Ar flow is 150-2The flow rate is 40-60sccm, the working pressure is 0.2-0.5Pa, the substrate negative bias is 180-220V, the ion source current is 2-5A, the titanium target current is 30-50A, and the sputtering time is 300-600 s; after the sputtering process is started, keeping other parameters unchanged, linearly increasing the current of a titanium target to the completion of sputtering by a control program, and depositing a TiN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiN gradient coating is 20-30 μm; introducing 40-60sccm methane, keeping other parameters unchanged, linearly reducing the current of the titanium target to the completion of sputtering by a control program, and depositing a TiCN gradient coating on the surface of the Co-based-WC coating, wherein the thickness of the TiCN gradient coating is 20-30 mu m; finally obtaining a Co-based-WC/TiN/TiCN 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 claim 5-6, wherein the process conditions of the sand blasting treatment of 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.
8. A method for repairing a cold-punching die according to any of claims 5 to 7, wherein the step (5) further comprises subjecting the Co-based-WC coating to an ion bombardment treatment after the preheating; the sputtering parameters are as follows: the rotation speed of the sample holder is 10-20r/min, the Ar flow is 100-150ccm, the working pressure is 0.1-0.3Pa, the negative bias of the substrate is 150-200V, and the sputtering time is 60-120 s.
9. A cold punching die repairing method according to any one of claims 6-8, wherein the linear increase of the titanium target current is specifically: i ist=I0+ (0.02-0.03) x t; the linear reduction of the titanium target current is specifically It ’=I。 ’-（0.01-0.02）×t。
10. A cold-punching die comprising the Co-based-WC/TiN/TiCN composite coating according to any one of claims 1 to 9 as a repair layer.
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CN111663093A (en) * 2020-06-05 2020-09-15 广东电网有限责任公司 Cermet material, cermet coating and preparation method thereof
CN112725792A (en) * 2020-12-28 2021-04-30 成都美奢锐新材料有限公司 Preparation method of chromium nitride-titanium carbonitride base metal ceramic composite coating
CN117587405A (en) * 2024-01-16 2024-02-23 宁波爱柯迪科技产业发展有限公司 Aluminum liquid adhesion-resistant anti-erosion composite coating for die casting die and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN111663093A (en) * 2020-06-05 2020-09-15 广东电网有限责任公司 Cermet material, cermet coating and preparation method thereof
CN112725792A (en) * 2020-12-28 2021-04-30 成都美奢锐新材料有限公司 Preparation method of chromium nitride-titanium carbonitride base metal ceramic composite coating
CN117587405A (en) * 2024-01-16 2024-02-23 宁波爱柯迪科技产业发展有限公司 Aluminum liquid adhesion-resistant anti-erosion composite coating for die casting die and preparation method thereof
CN117587405B (en) * 2024-01-16 2024-04-09 宁波爱柯迪科技产业发展有限公司 Aluminum liquid adhesion-resistant anti-erosion composite coating for die casting die and preparation method thereof

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