CN108070817B - Composite double treatment method for metal die steel surface - Google Patents

Composite double treatment method for metal die steel surface Download PDF

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CN108070817B
CN108070817B CN201611011000.7A CN201611011000A CN108070817B CN 108070817 B CN108070817 B CN 108070817B CN 201611011000 A CN201611011000 A CN 201611011000A CN 108070817 B CN108070817 B CN 108070817B
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die
vacuum chamber
treatment method
die steel
coating
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CN108070817A (en
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彭继华
苏东艺
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GUANGZHOU JINTAI SCIENCE AND TECHNOLOGY Co Ltd
South China University of Technology SCUT
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GUANGZHOU JINTAI SCIENCE AND TECHNOLOGY Co Ltd
South China University of Technology SCUT
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C23C8/38—Treatment of ferrous surfaces

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

Abstract

The invention provides a metal die steel surface composite double-treatment method, which comprises the following steps: cleaning the surface of the metal die steel, drying and pretreating the surface of the metal die steel, performing ion etching on the surface of the die steel in a vacuum chamber by adopting an auxiliary ion source, performing carbonitriding and carbonitriding on the die by adopting the auxiliary ion source, performing argon ion bombardment etching on the surface by adopting the auxiliary ion source, applying the surface to the die in an asymmetric bipolar pulse bias mode, coating a PVD coating by a cathodic arc discharge method and the like. The metal die steel surface composite double-treatment method can realize the reinforcement of full coverage and no dead angle of the die surface, and meanwhile, the PVD coating is coated by using a cathodic arc discharge method, the grooves and the blind holes receive and adsorb deposition particles through reasonable change of frequency and duty ratio, the surfaces of the blind holes and the narrow grooves on the die are further improved, and the PVD coating as thick as possible is obtained, so that the coating with high oxygen resistance and excellent wear resistance is prepared on the surface of the die.

Description

Composite double treatment method for metal die steel surface
Technical Field
The invention relates to metal surface treatment, in particular to a composite treatment technology for carrying out surface hardening treatment on die steel and obtaining a high-bonding-force wear-resistant corrosion-resistant film coating through physical vapor deposition.
Background
Metal substrate molds are important tools for large-scale mass production in modern advanced manufacturing industries. The working temperature is divided from the use time, the hot die, the cold die and the plastic die are adopted, and the selected die base materials are respectively hot die steel and cold die steel; from the viewpoint of the processing, there are a casting die, an extrusion die, and the like. Because of the working conditions of the die, in addition to the requirement of sufficient toughness, the die is required to have high surface wear resistance, adhesion resistance, scratch resistance and fatigue resistance. Therefore, the current general means is to adopt the surface treatment technology to meet the requirements of high wear resistance, bonding resistance, scratch resistance and fatigue resistance. The mold industry has developed and applied various surface treatment techniques such as electroplating/electroless plating, surface heat treatment (e.g., induction heating, laser treatment, etc.), surface metal diffusion treatment (e.g., Mo, V, etc.), surface non-metal diffusion treatment (e.g., molten C, N, O, S, Si, B, etc.), surface vapor deposition (including Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD)), etc., according to different use conditions. Considering the requirements of the performance of the die steel along with the temperature change and the stability of the die size, many of the above technologies which need to be implemented for a long time at more than 600 ℃ are not suitable for the surface treatment of high-precision dies, otherwise complicated post-treatment procedures such as tempering, size adjustment, grinding and the like are brought.
When the surface of the mold is nitrided by single ion, the treatment temperature is usually 500-600 ℃, the treatment time is long, and a compound layer (commonly called as "white layer") is usually formed on the surface of the nitrided layer (such as Chinese patent CN104178771A), so that the subsurface region is depleted of alloy elements. The white layer is easy to be a damage source of the nitriding coating in the using process. Although the C-N co-permeation (such as Chinese patent CN104152916A) can effectively inhibit the white and bright layer on the surface of the permeation layer, the hardness of the permeation layer is not more than HV 1300 at most, and the red hardness is poor, thereby limiting the further improvement of the service life of the die. The surface of the Chinese patent CN101058870A die adopts a single PVD coating, and the weak bonding force between the coating and the substrate and the poor mechanical matching between the PVD coating and the substrate are fatal factors for limiting the exertion of the advantages of high hardness, low friction coefficient and the like of the PVD coating. In the recently published patent CN103286919A, the example reports that the graphene film is directly prepared on the surface of the mold by using a high-temperature high-pressure CVD method, and the report does not describe the mold substrate, but it is inferred that the method is not suitable for being applied to steel-based molds, because the substrate on which graphene can grow on the CVD surface is mainly metal such as Cu/Ni/Ir/Au so far. Chinese patent CN102105243A is also a CVD method, which is essentially to form a C-S co-diffusion layer-carbon film containing nano-tubes/wires on the surface of a die-casting die, then to coat fullerene powder on the surface, and to cover the traditional release agent on the coating surface when in use, thereby improving the anti-aluminum-sticking capability of the die.
In conclusion, the surface hardness of the coating obtained by a Physical Vapor Deposition (PVD) method can reach more than HV2000, and even the super-hard coating is obtained; the temperature of the coating preparation process can be controlled to be lower than 500 ℃, so that the PVD coating has extremely high wear resistance and tensile damage resistance, and meets the requirement of a metal die on surface wear resistance; and the PVD preparation process basically cannot cause the change of the matrix structure, and the size of the die is not influenced. Therefore, PVD techniques have great potential in the area of mold surface treatment. However, the PVD coating is directly prepared on the surface of the die steel, and the PVD coating with high bonding force is difficult to obtain due to the fact that the hardness, the elastic modulus, the thermal expansion coefficient and the like of the base body are different from those of the PVD coating, and the PVD coating is prone to failure in the using process. On the other hand, geometrically complex molds tend to have blind holes with large depth to diameter ratios, or deep and narrow trenches, where it is difficult to obtain uniform coatings using PVD techniques alone, even in uncoated areas. Even if PVD coatings can fully exploit their advantages, die failure can easily start from blind holes, narrow grooves. In recent years, although some reports have been made at home and abroad about a process technology in which after ion nitriding is adopted on the surface of die steel or on dies (such as die-casting pins and the like) with simple curved surface shapes, the surface is polished to remove a white and bright layer, and then PVD treatment is carried out, the problem that the bonding matching between the white and bright layer generated by ion nitriding and a PVD layer is poor is still the main problem, and in order to solve the problem that the bonding force of the PVD coating is weak due to the white and bright layer, the white and bright layer is removed by polishing and sand blasting after ion nitriding. The white bright layer on the simple curved surface is easy to remove, deep holes and narrow grooves in the die are not easy to remove, and the white bright layer which is difficult to remove at the parts can be weak links in the service of the die. The surface treatment of the die is required to meet the following requirements, on one hand, the surface area of the working die, such as a simple plane, a curved surface, a deep hole surface and a narrow groove surface, is required to be fully strengthened after the surface treatment; on the other hand, the surface layer obtained by the treatment has high bonding strength with the substrate, and the coating has high hardness, high red hardness, high oxidation resistance and high thermal fatigue resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the invention is to provide a method for treating the surface of a die, which can realize the full coverage of the surface of the die and the strengthening without dead angles, and can also effectively realize the combination of low-temperature high-efficiency ion carbonitriding and physical vapor deposition with high film-substrate bonding strength and excellent wear resistance aiming at the characteristics of die steel and the characteristics of complex shape of the die.
In order to realize the technical scheme, the invention provides a metal die steel surface composite double-treatment method, which specifically comprises the following steps:
1) cleaning the surface of the metal die steel: removing oil stains on the surface of the die steel by using a commercially available metal cleaning agent, rinsing and drying for later use;
2) drying and pretreating the surface of the metal die steel: fixing the rinsed and dried die steel on a workpiece rack of a Hauzer device, closing a vacuum chamber door, starting the workpiece rack to rotate, and pumping the vacuum chamber to a vacuum degree lower than 5x10-3Pa, starting the auxiliary heating device, and heating the vacuum chamber containing the die steel to 300-400 ℃;
3) and (3) carrying out ion etching on the surface of the die steel in the vacuum chamber by adopting an auxiliary ion source: argon is introduced into an argon ion beam obtained by a hot wire direct current arc ion source, so that the pressure of a vacuum chamber is 0.1Pa, the beam current is 70-100A, a bias voltage of 200V is applied to the die steel, and the surface of the die steel is bombarded and etched for 30-90 minutes by using a direct current bias mode;
4) adopting an auxiliary ion source to realize carbonitriding on the die: keeping the temperature in the vacuum chamber at 400 ℃ at 300-;
5) after carbonitriding, performing argon ion bombardment etching on the surface by using an auxiliary ion source;
6) and applying the asymmetric bipolar pulse bias mode to the die, and coating the PVD coating by a cathodic arc discharge method.
Preferably, the specific steps of preparing the PVD coating by the cathodic arc discharge method in step 6) are as follows:
61) introducing nitrogen into the vacuum chamber to keep the pressure of the vacuum chamber at 0.5-1 Pa;
62) starting an asymmetric bipolar pulse bias mode, wherein the frequency is 300-30kHz, the negative pulse peak value is 50-150V, the positive pulse peak value is 10-20V, and the duty ratio is 30-80%;
63) opening a pure metal cathode electric arc target, and closing the metal cathode electric arc target after preparing a binary nitride layer with the thickness of 0.5-1.0 micron by using the target current of 100-120A;
64) opening the aluminum-rich alloy cathode electric arc target, and closing the alloy target after preparing the 3-4 micron thick multi-element nitride layer with the target current of 100-120A;
65) and after the temperature of the vacuum chamber is cooled to be below 100 ℃, opening the door of the vacuum chamber, and taking out the workpiece.
In the technical scheme, the PVD coating preparation device is a conventional technology, and a Dutch HAUZERflex-850 vacuum coating device (hereinafter referred to as HAUZER device) is adopted. The metal die steel surface composite double treatment method realizes low-temperature ion carbonitriding on the surface of a die at the temperature lower than 400 ℃ by the aid of a high-density ion source to obtain a 30-50 micron thick carburized layer, so that the surface hardness of the die exceeds HV 1000; meanwhile, carbonitriding avoids a white bright layer, the hardness and the elastic modulus of the carburized layer are reduced in a slow gradient manner from the surface to the core substrate, and the problem that the PVD coating is poor in binding force due to the white bright layer in the nitrided layer in the prior report is solved; the PVD coating is coated by using a cathodic arc discharge method, the receiving and adsorption of the grooves and the blind holes to deposited particles are enhanced through reasonable change of frequency and duty ratio, and the surfaces of the blind holes and the narrow grooves on the die are further improved to obtain the PVD coating as thick as possible; thereby preparing a coating with high oxygen resistance and excellent wear resistance on the surface of the die.
Preferably, the carbonitriding in step 4) uses a mixed working gas of nitrogen, methane and hydrogen, wherein the volume percentage of methane gas is 10-25%, the volume percentage of hydrogen is 40-60%, and the balance is nitrogen.
Preferably, the argon ion etching time after the carbon and nitrogen ions are co-diffused in the step 5) is 15-30 minutes, and the beam current is 70-100A.
Preferably, the PVD coating prepared in step 6) is a composite coating of a binary nitride and a polynary nitride.
Preferably, the binary nitride is one of TiN or CrN.
Preferably, the multi-component nitride is aluminum-rich Al-Me-N nitride, wherein Me is at least one of Cr and Ti, and can contain one of V, Si, Nb and Y.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention realizes the full coverage strengthening of the working area of the die with the complex shape, and the solution is to adopt a high-density ion source for assistance, realize the low-temperature ion carbonitriding on the surface of the die at the temperature lower than 400 ℃, obtain a 30-50 micron thick carburized layer, and ensure that the hardness of the surface of the die exceeds HV 1000; the plasma-assisted carbonitriding can cover areas such as surface holes and narrow grooves with complex shapes.
(2) The invention solves the problem of poor bonding force of the PVD coating caused by the existence of the white bright layer in the existing nitriding layer, and the solution is to adopt reasonable carbonitriding to avoid the occurrence of the white bright layer, and the hardness and the elastic modulus of the nitriding layer are reduced in a slow gradient from the surface to the core substrate.
(3) The invention aims to further improve the surfaces of blind holes and narrow grooves on a die to obtain a PVD coating as thick as possible, and the solution is that bipolar pulse bias voltage is applied to the surface of a workpiece when the PVD coating is prepared, the receiving and adsorption of the grooves and the blind holes on deposited particles are enhanced through reasonable change of frequency and duty ratio, and the coating with high oxygen resistance and excellent wear resistance is prepared on the surface of the die.
Drawings
FIG. 1 is a schematic diagram of the steps of the treatment method of the present invention.
Detailed Description
For a better understanding of the present invention, the following detailed description is given in conjunction with the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
A composite double treatment method for a metal die steel surface is shown in figure 1, and specifically comprises the following steps:
1) selecting an H13 steel polishing and sand blasting test piece (subjected to quenching and double annealing treatment, and the hardness of HRC50) and placing the test piece into an aqueous solution containing 5 wt% of a commercially available 'super-strong' metal degreasing cleaning agent, boiling for about 5 minutes, rinsing the test piece with deionized water, soaking the test piece in 100mL/L deionized water solution containing an antirust 1063 reagent of German Bohr company for 10 seconds, taking out the test piece, drying the test piece with oilless compressed air, and drying the test piece for 1 hour at 80 ℃ for later use; the test piece is hung on a fixture and put into a HAUZER device;
2) closing the vacuum chamber door and starting the workpiece rack to rotate; the vacuum chamber was evacuated to a background vacuum of 5x10-3After Pa, starting an auxiliary heating device, and heating the vacuum chamber to 300 ℃;
3) argon is introduced to ensure that the pressure of the vacuum chamber is 0.1Pa and the beam current is 70A; applying a bias voltage of 200V to the workpiece, and adopting a direct-current bias mode; bombarding and etching the surface of the mold for 30 minutes by using argon ions;
4) maintaining the argon flow and the ion beam current of the hot wire direct current arc ion source in the step 3); introducing mixed working gas of nitrogen, methane and hydrogen into the vacuum chamber, wherein the volume percentage of the methane gas is 10%, the volume percentage of the hydrogen gas is 40%, and the balance is nitrogen; after the vacuum of the vacuum chamber reaches 2.0Pa, the direct current bias voltage of the workpiece is adjusted to 400V direct current, and glow discharge occurs on the surface of the die; controlling carbonitriding for 1 hour (obtaining a carburized layer with the thickness of 45 micrometers), closing the mixed working gas, adjusting the direct-current bias voltage of the mold to be 150V, and closing the ion source after argon ions bombard the surface of the mold for 15 minutes;
5) introducing nitrogen into the vacuum chamber to keep the pressure of the vacuum chamber at 0.5 Pa; starting an asymmetric bipolar pulse bias mode, wherein the frequency is 300Hz, the peak value of negative pulse is 150V, the peak value of positive pulse is 20V, and the duty ratio is 30%; starting a cathode electric arc Cr target, wherein the target current is 100A, and closing the electric arc target after 0.5 micron CrN is prepared; opening Al70Cr30Alloy cathode electric arc target, target current 100A, preparation of 3 micron thick Al70Cr30And closing the alloy target after N layers. And after the temperature of the vacuum chamber is cooled to 100 ℃, opening the door of the vacuum chamber, and taking out the workpiece.
The coating was visually observed to be uniform and dense. The coating-to-substrate bond after the rockwell indentation evaluation treatment was HF 1.
The H13 steel surface area obtained after the treatment is fully strengthened on simple planes, curved surfaces, deep hole surfaces and narrow groove surfaces; meanwhile, the PVD coating obtained by the treatment has high bonding strength with an H13 steel substrate, and the hardness, red hardness, oxidation resistance and thermal fatigue resistance of the H13 steel are improved through the PVD coating.
Example 2
A composite double treatment method for a metal die steel surface is shown in figure 1, and specifically comprises the following steps:
1) selecting an M35 steel polishing and sand blasting test piece (subjected to quenching and double annealing treatment, and the hardness of HRC62) and placing the test piece into an aqueous solution containing 5 wt% of a commercially available 'super-strong' metal degreasing cleaning agent, boiling for about 5 minutes, rinsing the test piece with deionized water, soaking the test piece in 100mL/L deionized water solution containing an antirust 1063 reagent of German Bohr company for 5 seconds, taking out the test piece, drying the test piece with oilless compressed air, and drying the test piece for 1 hour at 80 ℃ for later use; the test piece is hung on a fixture and put into a HAUZER device;
2) closing the vacuum chamber door and starting the workpiece rack to rotate; the vacuum chamber was evacuated to a background vacuum of 7x10-3After Pa, starting an auxiliary heating device, and heating the vacuum chamber to 400 ℃;
3) argon is introduced to ensure that the pressure of the vacuum chamber is 0.1Pa and the beam current is 100A; applying a bias voltage of 200V to the workpiece, and adopting a direct-current bias mode; bombarding and etching the surface of the mold for 60 minutes by using argon ions;
4) maintaining the argon flow and the ion beam current of the hot wire direct current arc ion source in the step 3); introducing mixed working gas of nitrogen, methane and hydrogen into the vacuum chamber, wherein the volume percentage of the methane gas is 25%, the volume percentage of the hydrogen gas is 55%, and the balance is nitrogen; after the vacuum of the vacuum chamber reaches 5.0Pa, the direct current bias voltage of the workpiece is adjusted to 600V direct current, and glow discharge occurs on the surface of the die; controlling carbonitriding for 40 minutes (obtaining a carburized layer with the thickness of 60 micrometers), closing the mixed working gas, adjusting the direct-current bias voltage of the mold to be 150V, and closing the ion source after argon ions bombard the surface of the mold for 20 minutes;
5) introducing nitrogen into the vacuum chamber to keep the pressure of the vacuum chamber at 1 Pa; starting an asymmetric bipolar pulse bias mode, wherein the frequency is 30kHz, the peak value of negative pulse is 50V, the peak value of positive pulse is 10V, and the duty ratio is 80%; starting a cathode arc Ti target, wherein the target current is 120A, and closing the arc target after preparing TiN with the thickness of 1 micron; opening Al65Cr35Alloy cathode electric arc target, target current 100A, preparation of 4 micron thick Al65Cr35And closing the alloy target after N layers. And after the temperature of the vacuum chamber is cooled to 100 ℃, opening the door of the vacuum chamber, and taking out the workpiece.
The coating was visually observed to be uniform and dense. The coating-to-substrate bond after the rockwell indentation evaluation treatment was HF 1.
The surface area of the M35 steel obtained by the treatment is fully strengthened in a simple plane, a curved surface, a deep hole surface and a narrow groove surface; meanwhile, the PVD coating obtained by the treatment has high bonding strength with an M35 steel substrate, and the hardness, red hardness, oxidation resistance and thermal fatigue resistance of the H13 steel are improved through the PVD coating.
Example 3
A composite double treatment method for a metal die steel surface is shown in figure 1, and specifically comprises the following steps:
1) an extrusion die 1 sleeve of a mobile phone shell piece is manufactured by H13 (through quenching and double annealing treatment, the hardness is HRC50), an H13 die steel polishing test piece with the same hardness is placed in an automatic cleaning line of the Jintai company for cleaning, the cleaned workpiece is rinsed by deionized water and soaked in 100mL/L deionized water solution containing an antirust 1063 reagent of the German Borl company for 15 seconds, the workpiece is taken out and dried by oilless compressed air for drying at 80 ℃ for 1 hour for later use; hanging a workpiece on a fixture and putting the workpiece into a HAUZER device;
2) closing the vacuum chamber door and starting the workpiece rack to rotate; the vacuum chamber was evacuated to a background vacuum of 5x10-3After Pa, starting an auxiliary heating device, and heating the vacuum chamber to 400 ℃;
3) argon is introduced to ensure that the pressure of the vacuum chamber is 0.1Pa and the beam current is 90A; applying a bias voltage of 200V to the workpiece, and adopting a direct-current bias mode; bombarding and etching the surface of the mold for 90 minutes by using argon ions;
4) maintaining the argon flow and the ion beam current of the hot wire direct current arc ion source in the step 3); introducing mixed working gas of nitrogen, methane and hydrogen into the vacuum chamber, wherein the volume percentage of the methane gas is 15%, the volume percentage of the hydrogen gas is 45%, and the balance is nitrogen; after the vacuum of the vacuum chamber reaches 3.5Pa, the direct current bias voltage of the workpiece is adjusted to be 500V direct current, and glow discharge occurs on the surface of the die; controlling carbonitriding for 30 minutes (obtaining a carburized layer with the thickness of 43 microns), closing the mixed working gas, adjusting the direct-current bias voltage of the mold to be 150V, and closing the ion source after argon ions bombard the surface of the mold for 30 minutes;
5) introducing nitrogen into the vacuum chamber to keep the pressure of the vacuum chamber at 0.6 Pa; starting an asymmetric bipolar pulse bias mode, wherein the frequency is 10kHz, the peak value of negative pulse is 80V, the peak value of positive pulse is 15V, and the duty ratio is 50%; starting a cathode electric arc Cr target, wherein the target current is 120A, and closing the electric arc target after CrN with the thickness of 1 micron is prepared; opening Al65Cr35Alloy cathode electric arc target, target current 100A, preparation of 3.5 micron thick Al65Cr35And closing the alloy target after N layers. And after the temperature of the vacuum chamber is cooled to 70 ℃, opening the door of the vacuum chamber, and taking out the workpiece.
The coating was visually observed to be uniform and dense. The coating-to-substrate bond after the rockwell indentation evaluation treatment was HF 1.
The above description is only for the preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, and therefore, all equivalent or modifications that do not depart from the spirit of the present invention are intended to fall within the scope of the present invention.

Claims (7)

1. A composite double treatment method for the steel surface of a metal die is characterized by comprising the following steps:
1) cleaning the surface of the metal die steel;
2) drying and pretreating the surface of the metal die steel;
3) and (3) carrying out ion etching on the surface of the die steel in the vacuum chamber by adopting an auxiliary ion source: argon is introduced into an argon ion beam obtained by a hot wire direct current arc ion source, so that the pressure of a vacuum chamber is 0.1Pa, the beam current is 70-100A, a bias voltage of 200V is applied to the die steel, and the surface of the die steel is bombarded and etched for 30-90 minutes by using a direct current bias mode;
4) adopting an auxiliary ion source to realize carbonitriding on the die: keeping the temperature in the vacuum chamber at 400 ℃ at 300-;
5) after carbonitriding, performing argon ion bombardment etching on the surface by using an auxiliary ion source;
6) applying an asymmetric bipolar pulse bias mode to a die, and coating a PVD coating by a cathodic arc discharge method, which comprises the following steps:
61) introducing nitrogen into the vacuum chamber to keep the pressure of the vacuum chamber at 0.5-1 Pa;
62) starting an asymmetric bipolar pulse bias mode, wherein the frequency is 300-30kHz, the negative pulse peak value is 50-150V, the positive pulse peak value is 10-20V, and the duty ratio is 30-80%;
63) opening a pure metal cathode electric arc target, and closing the metal cathode electric arc target after preparing a binary nitride layer with the thickness of 0.5-1.0 micron by using the target current of 100-120A;
64) opening the aluminum-rich alloy cathode electric arc target, and closing the alloy target after preparing the 3-4 micron thick multi-element nitride layer with the target current of 100-120A;
65) and after the temperature of the vacuum chamber is cooled to be below 100 ℃, opening the door of the vacuum chamber, and taking out the workpiece.
2. The metal mold steel surface composite double treatment method according to claim 1, characterized in that: the method for drying and pretreating the surface of the metal die steel in the step 2) is to fix the rinsed and dried die steelOn the workpiece holder, the door of the vacuum chamber is closed, the workpiece holder is started to rotate, and the vacuum chamber is pumped to the vacuum degree lower than 5x10-3Pa, starting the auxiliary heating device, and heating the vacuum chamber containing the die steel to 300-400 ℃.
3. The metal mold steel surface composite double treatment method according to claim 1, characterized in that: the carbon and nitrogen ion co-permeation in the step 4) adopts mixed working gas of nitrogen, methane and hydrogen, wherein the volume percentage of the methane gas is 10-25%, the volume percentage of the hydrogen is 40-60%, and the balance is the nitrogen.
4. The metal mold steel surface composite double treatment method according to claim 1, characterized in that: the etching time of the argon ions after the carbon and nitrogen ions are co-diffused in the step 5) is 15-30 minutes, and the beam current is 70-100A.
5. The metal mold steel surface composite double treatment method according to claim 1, characterized in that: the PVD coating prepared in the step 6) is a composite coating of binary nitride and polynary nitride.
6. The metal mold steel surface composite double treatment method according to claim 5, characterized in that: the binary nitride is one of TiN or CrN.
7. The metal mold steel surface composite double treatment method according to claim 5, characterized in that: the multi-component nitride is Al-Me-N nitride rich in aluminum, wherein Me is at least one of Cr and Ti and contains one of V, Si, Nb and Y.
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CN108893707A (en) * 2018-07-23 2018-11-27 江苏苏德涂层有限公司 Aluminium die casting surface coated treatment technique and the cated aluminium die casting of tool
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CN104911552A (en) * 2015-06-25 2015-09-16 西安交通大学 Method for reinforcing surface of hot-extrusion die through cementation compounding
CN105132876A (en) * 2015-09-15 2015-12-09 辽宁科技大学 Surface compound treatment method for steel gear
CN106011738A (en) * 2016-06-16 2016-10-12 常州普威特涂层有限公司 Surface plating composite coating process for die

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CN105132876A (en) * 2015-09-15 2015-12-09 辽宁科技大学 Surface compound treatment method for steel gear
CN106011738A (en) * 2016-06-16 2016-10-12 常州普威特涂层有限公司 Surface plating composite coating process for die

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