CN108396292B - Composite coating for die-casting die and preparation method thereof - Google Patents
Composite coating for die-casting die and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/20—Accessories: Details
- B22D17/22—Dies; Die plates; Die supports; Cooling equipment for dies; Accessories for loosening and ejecting castings from dies
- B22D17/2209—Selection of die materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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Abstract
The invention provides a high-hardness and high-toughness gradient composite coating suitable for high-temperature resistance and self-lubrication of a die-casting die and a preparation method thereof, wherein the gradient composite coating consists of a bonding layer, a transition layer, a supporting layer and a functional layer which are deposited on a die substrate and are sequentially stacked from inside to outside; the bonding layer is a Cr bonding layer for improving the bonding force between the composite coating and the surface of the die; the transition layer is formed by compounding a CrN transition layer and a CrAlN transition layer; the supporting layer is formed by correspondingly and alternately superposing CrAlSiN layers and CrAlVN layers; the functional layer is formed by correspondingly and alternately superposing CrAlSiCN layers and CrAlVCN layers. The composite material has good surface hardness, wear resistance, high-temperature oxidation resistance and corrosion resistance, has better self-lubricating effect, can obviously reduce the deformation of the die, improves the precision of the die, eliminates the fatigue failure of the die coating, prolongs the service life, and is suitable for the development of the die with complex modeling.
Description
Technical Field
The invention relates to the technical field of preparation of coatings and die-casting molds, in particular to a high-hardness and high-toughness gradient composite coating suitable for high-temperature resistance self-lubrication of a die-casting mold and a preparation method for depositing the gradient composite coating.
Background
The die-casting die is a large class of dies, and in the current era of rapid industrial development, the die-casting die is new along with the development of the automobile industry, but also meets new challenges. When the large-scale die-casting die with the complex shape needs to be in direct contact with high-temperature molten metal, the die-casting die is easy to deform, and the efficiency, the precision and the service life of the die still need to be improved at present.
The main problems faced by die casting molds include the following: the working environment is at high temperature, the mould is deformed, and the precision of the mould with complex modeling can be seriously influenced; the manufacturing cycle of the die-casting die is long, but the service life is influenced by the surface failure of the die and is difficult to achieve the expected service life; the surface of the high-hardness die with small deformation has poor lubricating effect, and the surface of the product is damaged in the demolding process. Therefore, in order to prevent the die-casting mold from losing efficacy, the surface of the mold is required to have properties such as high hardness, heat corrosion resistance, adhesion resistance, impact resistance and the like.
In recent years, various new surface treatment techniques for die casting molds, such as surface treatment techniques by means of conventional metal heat treatment processes, have been developed; surface modification technology including surface thermal diffusion treatment, surface phase change strengthening and the like; surface coating technology mainly using vapor deposition. The physical vapor deposition technology in the coating technology category is a hot spot of recent research on manufacturing hard coatings on the surfaces of metal materials, the two methods of arc ion plating and magnetron sputtering are mature in industrial application, and common coating materials include various metal nitrides such as TiN, CrN, TiAlN and the like.
However, the coating is difficult to meet the requirements of die products on hardness, wear resistance and service life, and has a plurality of technical problems in the aspect of prolonging the service life of die-casting dies in large-scale production, mainly comprising improving the toughness of the coating body, improving the lubricity of the coating, improving the bonding force of a hard film layer and a substrate, and the like.
Disclosure of Invention
The invention aims to provide a high-hardness and high-toughness gradient composite coating which is suitable for high-temperature resistance and self-lubrication of a die-casting die.
It is another object of the present invention to provide a method of depositing the gradient composite coating described above.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a composite coating for die casting die comprises a bonding layer, a transition layer, a supporting layer and a functional layer which are deposited on a die matrix and are sequentially stacked from inside to outside;
the bonding layer is a Cr bonding layer for improving the bonding force between the composite coating and the surface of the die;
the transition layer is formed by compounding a CrN transition layer and a CrAlN transition layer, and the CrN transition layer is positioned between the Cr bonding layer and the CrAlN transition layer;
the supporting layer is of a multilayer structure formed by alternately overlapping and compounding CrAlSiN layers and CrAlVN layers, and the CrAlVN layers are positioned on the CrAlN transition layers and alternately overlapped with the CrAlSiN layers;
the functional layer is of a multilayer structure formed by alternately overlapping and compounding CrAlSiCN layers and CrAlVCN layers, and the CrAlVCN layers are positioned on the outermost CrAlSiN layers and are alternately overlapped with the CrAlSiCN layers.
Further, in the CrAlN layer, Al atom percentage is 20-40 at%;
and/or the presence of a gas in the gas,
the thickness of the CrN layer is 200-400nm, and the thickness of the CrAlN layer is 100-200 nm.
Further, the atomic percent of Si in the single layer of the CrAlSiN layer in the supporting layer is 5-10at.%, and the atomic percent of Al is 20-30 at.%; the atomic percent of V in the CrAlVN layer of the monolayer is 7-12at.%, and the atomic percent of Al is 20-30 at.%;
and/or the presence of a gas in the gas,
in one period of the supporting layer, the thickness of the CrAlVN layer is 20-40nm, the thickness of the CrAlSiN layer is 10-20nm, and the total thickness of the supporting layer is 300-600 nm.
Furthermore, in the functional layer, the CrAlSiCN layer and the CrAlVCN layer are respectively made of (CrAl, CrV) N nanocrystals embedded in amorphous Si3N4And a crystal structure in which amorphous C atoms are doped in the gap;
the functional layer comprises the following layers in atomic percentage: 15-30 at.% Cr, 10-20 at.% Al, 7-12at.% V, 5-10at.% Si, 3-5 at.% C, 40-49 at.% N;
and/or the presence of a gas in the gas,
the thickness of the functional layer is 2-3 μm.
Further, the thickness of the Cr bonding layer is 100-200 nm.
The invention provides a method for preparing the composite coating deposited on the surface of a die-casting die, which comprises the following steps:
1) glow cleaning, namely putting the pretreated mould substrate into vacuum cathode arc ion plating equipment, vacuumizing and heating until the surface temperature of the substrate reaches 300-500 ℃, controlling the air pressure to be 1.0-1.5Pa, and filling Ar gas for glow discharge cleaning;
2) preparing a Cr layer, adjusting the vacuum pressure to 1/2-2/3 of the pressure in glow cleaning, starting a metal Cr target position, and depositing a Cr bonding layer;
3) preparing CrN transition layer, reducing bias voltage, and introducing N2The mixed gas with Ar is controlled to have the pressure of 0.5-1.2Pa, the substrate temperature is 300-;
4) preparing a CrAlN transition layer, closing a metal Cr target position, opening a CrAl alloy target position, keeping bias voltage unchanged, and introducing N2Maintaining the air pressure at 0.5-1.2Pa, the matrix temperature at 300-500 ℃, and depositing a CrAlN transition layer;
5) preparing a supporting layer, simultaneously opening CrAl, CrV and CrSi target positions, and introducing N2Keeping the air pressure at 0.8-3.0Pa and the matrix temperature at 300-;
6) preparing a functional layer, keeping the target positions of CrAl, CrV and CrSi open, and introducing Ar and N2Intermittently introducing C while introducing the mixed gas2H2The vacuum degree is kept at 0.8-3.0Pa, the matrix temperature is 300-.
Further, in the step 1), when the glow discharge cleaning is carried out, the anode layer ion source voltage is started at 600V, the current is 3-5A, the substrate frame rotating speed is 1-3rpm, the negative bias is-900V, and the bombardment time is 60-80 min;
and/or the presence of a gas in the gas,
in the step 2), starting a metal Cr target position, controlling the current to be 60-90A, controlling the negative bias voltage to be-300V, and depositing for 2-10 min.
Further, in the step 3) and the step 4), the rotating speed of the substrate frame is kept at 1-3rpm, the current is controlled at 70-100A, and the duty ratio is 60-80%;
the deposition time of the CrN transition layer is 20-30min, and the deposition time of the CrAlN transition layer is 10-20 min.
Further, in the step 5), the output current of each target is controlled to be 70-100A, the negative bias voltage is 60-120V, and the duty ratio is 50-80%;
during alternate deposition, the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target and 2-3rpm when passing through a CrSi target, and the deposition time is 30-60min totally.
Further, in the step 6), the output current of each target is controlled to be 70-100A, and each time Ar gas and N are introduced2Introducing 1minC at the same time when the mixed gas is 4min2H2(ii) a Controlling the negative bias voltage to be 60-120V and the duty ratio to be 50-80%;
during alternate deposition, the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target and 1.5-2rpm when passing through a CrSi target, and the deposition time is 80-120min totally.
The high-hardness and high-toughness gradient composite coating for the high-temperature-resistant self-lubricating of the die-casting die, provided by the invention, has the advantages of good surface hardness, wear resistance, high-temperature oxidation resistance and corrosion resistance, better self-lubricating effect, capability of obviously reducing die deformation, improving die precision, eliminating fatigue failure of the die coating, prolonging service life and suitability for development of dies with complex shapes. Tests prove that the composite gradient coating has the bonding force exceeding 65N, the internal stress less than 0.15Gpa and the hardness higher than 35GPa, and the service life is more than 3 times of that of a common die-casting die.
Drawings
FIG. 1 is a schematic structural diagram of a gradient structure composite coating according to the present invention;
FIG. 2 is a schematic structural view of a magnetron sputtering apparatus for depositing the inventive coating.
1. The die comprises a die base body, 2. a Cr bonding layer, 3. a CrN layer, 4. a CrAlN layer, 5.a CrAlVN layer, 6. a CrAlSiN layer, 7. a CrAlVCN layer and 8. a CrAlSiCN layer;
9. vacuum chamber, 10, base station, 11, Cr target12.CrAl alloy target, 13.CrV alloy target, 14.CrSi alloy target, 15.Ar gas circuit, 16.N2Gas path, 17.C2H2And (6) air channels.
Detailed Description
The technical problems, solutions and advantages of the present invention have been clarified by referring to exemplary embodiments. However, the present invention is not limited to the exemplary embodiments disclosed below, and may be implemented in various forms.
A composite coating for die-casting die is shown in figure 1 and comprises a Cr combination layer, a CrN transition layer, a CrAlN transition layer, a supporting layer and a functional layer which are laminated from inside to outside and coated on the surface layer of a matrix, wherein the Cr combination layer can improve the binding force between the composite coating and the surface of a die, the transition layer formed by combining the CrN layer and the CrAlN layer can reduce the internal stress caused by lattice mismatching between the supporting layer and the combination layer, the structural toughness is enhanced, the binding strength of the supporting layer is improved, and the binding condition of the coating and the matrix is improved. The supporting layer is formed by alternately stacking a plurality of CrAlSiN layers and CrAlVN layers, so that the structural hardness can be improved, and the internal stress of a surface functional layer can be reduced. The functional layer is formed by correspondingly and alternately superposing CrAlSiCN layers and CrAlVCN layers, has high hardness, self-lubricating property and high temperature resistance, and can obviously prolong the service life of the die-casting die.
In the CrAlSiN/CrAlVN supporting layer with the periodic structure, CrSiN crystals have high hardness, and CrVN crystals can refine grains of the supporting layer and improve the hardness and toughness of the supporting layer. Compared with a high-hardness transition metal nitride coating without C element, the functional layer formed by compounding the CrAlSiCN layer and the CrAlVCN layer which are formed by nanocrystalline and amorphous, which effectively improves the hardness and chemical stability of the coating, enhances the hardness, wear resistance, high-temperature oxidation resistance and corrosion resistance of the surface of the die-casting die, has better self-lubricating effect, is beneficial to reducing die deformation, improves die precision, eliminates fatigue failure of the die coating, prolongs the service life and is beneficial to developing a complex modeling die. The gradient structure of the whole coating enables the mechanical properties of the substrate and the coating to be uniformly transited, and the internal stress of the coating is reduced.
The thickness of each layer is set according to the material composition of each layer, and according to the use characteristics of the coating.
Preferably, the Cr bonding layer is generally provided to a thickness of 100-200 nm.
In the CrAlN layer, the Al atom percent is 20-40 at.%; the thickness of the CrN layer is generally set to 200-400nm, and the thickness of the CrAlN layer is set to 100-200 nm.
The transition mode can obtain the optimal film-substrate bonding force. The thickness of each transition layer is set, so that excellent film-substrate binding force can be obtained, and the supporting and functional effects of a subsequent coating system are not influenced.
The supporting layer is of a multilayer structure formed by correspondingly and alternately superposing CrAlVN layers and CrAlSiN layers, wherein Si atomic percent in a single-layer CrAlSiN layer is 5-10at.%, and Al atomic percent is 20-30 at.%; the atomic percent of V in the CrAlVN layer of the monolayer is 7-12at.%, and the atomic percent of Al is 20-30 at.%.
In one period of the support layer, the thickness of the CrAlVN layer is preferably 20-40nm, the thickness of the CrAlSiN layer is preferably 10-20nm, and the total thickness of the support layer is preferably 300-600 nm.
In the functional layer, the CrAlSiCN layer and the CrAlVCN layer are respectively made of (CrAl, CrV) N nanocrystals embedded in amorphous Si3N4And amorphous C atoms are doped in the gaps. The functional layers are of a multilayer structure formed by correspondingly and alternately superposing CrAlSiCN layers and CrAlVCN layers, and the atomic percentages of each layer of the functional layer are as follows: 15-30 at.% Cr, 10-20 at.% Al, 7-12at.% V, 5-10at.% Si, 3-5 at.% C, 40-49 at.% N, preferably providing the functional layer with a thickness of 2-3 μm.
The method for depositing the composite coating on the surface of the die-casting die comprises the following steps:
glow cleaning, namely putting the pretreated mould substrate into vacuum cathode arc ion plating equipment, vacuumizing and heating until the surface temperature of the substrate reaches 300-500 ℃, controlling the air pressure to be 1.0-1.5Pa, and filling Ar gas for glow discharge cleaning; when the glow discharge cleaning is carried out, the anode layer ion source voltage is started at 500-600V, the current is 3-5A, the substrate frame rotating speed is 1-3rpm, the negative bias voltage is-900V, and the bombardment time is 60-80 min.
Preparing a Cr layer, adjusting the vacuum pressure to 1/2-2/3 of the pressure in glow cleaning, starting a metal Cr target, controlling the current to be 60-90A, controlling the negative bias to be-300V, depositing for 2-10min, and depositing a Cr bonding layer.
Preparing CrN transition layer, reducing bias voltage, and introducing N2Controlling the pressure of the mixed gas with Ar to be 0.5-1.2Pa, controlling the temperature of the substrate to be 300-.
Preparing a CrAlN transition layer, closing a metal Cr target position, opening a CrAl alloy target position, keeping bias voltage unchanged, and introducing N2Keeping the air pressure at 0.5-1.2Pa, the substrate temperature at 300-500 ℃, the rotation speed of the substrate frame at 1-3rpm, controlling the current at 70-100A and the duty ratio at 60-80%, and depositing the CrAlN transition layer for 10-20 min.
Preparing a supporting layer, simultaneously opening CrAl, CrV and CrSi target positions, and introducing N2Keeping the air pressure at 0.8-3.0Pa, the substrate temperature at 300-500 ℃, and controlling the output current of each target at 70-100A, the negative bias at 60-120V and the duty ratio at 50-80%; keeping the base station rotating, and alternately depositing a CrAlVN layer and a CrAlSiN layer, wherein the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target, 2-3rpm when passing through a CrSi target, and the deposition time is 30-60min totally.
Preparing a functional layer, keeping the target positions of CrAl, CrV and CrSi open, and introducing Ar and N2Intermittently introducing C while introducing the mixed gas2H2The vacuum degree is maintained at 0.8-3.0Pa, the substrate temperature is 300-2Introducing 1minC at the same time when the mixed gas is 4min2H2(ii) a Controlling the negative bias voltage to be 60-120V and the duty ratio to be 50-80%, rotating the workpiece on a base station, alternately depositing a CrAlSiCN layer and a CrAlVCN layer according to a preset rotating speed, wherein the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target, 1.5-2rpm when passing through a CrSi target, and the deposition rate is 1.5-2rpmThe accumulation time is 80-120 min.
Wherein, as shown in fig. 2, when the composite coating deposition is carried out to the die casting die, a Cr target 11, a CrAl alloy target 12, a CrV alloy target 13 and a CrSi alloy target 14 are uniformly distributed around the vacuum chamber 9, a base 10 is arranged at the center, a sample piece is arranged on the base 10, an Ar gas circuit 15 and an N gas circuit 15 are respectively arranged at one side of the vacuum chamber 92 Gas paths 16 and C2H2The gas path 17 separately fills Ar gas, nitrogen gas and acetylene into the vacuum chamber 9. And when the sample piece rotates along with the base station 10 on the base station 10, the sample piece is bombarded by the target sample pieces arranged around the sample piece, and the composite coating is deposited layer by layer.
The first embodiment is as follows:
from H13The working surface of a die-casting die base body made of the die steel material is subjected to polishing treatment, and the die base body is subjected to oil removal, wax removal, cleaning and drying by adopting an ultrasonic cleaning method.
Placing the cleaned and dried mould matrix in a vacuum cathode ion plating equipment cavity, heating to 400 ℃, and vacuumizing to 5 multiplied by 10-3Pa, introducing Ar to maintain the air pressure at 1.2Pa, starting the anode layer ion source, carrying out current of 3A, rotating the substrate frame at 1rpm, carrying out negative bias of-900V, and carrying out bombardment for 60 min.
After glow cleaning, vacuum adjusting to 0.8Pa, opening a metal Cr target, keeping the bias voltage at-300V and the current at 75A, and depositing for 10min to obtain a Cr metal interface bonding layer with the thickness of 120 nm.
After the Cr bonding layer deposition is finished, the bias voltage is reduced to-150V, and N is introduced2Controlling the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, the substrate frame rotating speed at 1rpm and the current at 80A, starting to deposit the CrN transition layer, and depositing for 15min to obtain the CrN transition layer with the thickness of 260 nm.
Closing the Cr target, opening the CrAl alloy target, keeping the bias voltage at-150V, controlling the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, the substrate frame rotating speed at 1rpm, and the current at 70A, depositing a CrAlN transition layer for 10min, and the thickness is 190 nm.
And after the deposition of the transition layer is finished, opening a CrV target, a CrAl target and a CrSi target, keeping the bias voltage at-150V, controlling the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, keeping the rotating speed of the substrate frame at 1.5rpm, keeping the CrV target current at 70A, the CrAl target current at 80A and the CrSi target current at 60A, and depositing for 20min to obtain a CrAlSiN/CrAlVN supporting layer with the thickness of 350 nm.
Continuously introducing 1minC every 5min2H2And keeping the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, keeping the rotating speed of the substrate frame at 1.5rpm, the CrV target current at 70A, the CrAl target current at 80A and the CrSi target current at 60A, and depositing for 120min to obtain a CrAlSiCN/CrAlVCN functional layer with the thickness of 3 mu m. And (4) turning off all target power supplies, stopping all gas, cooling the mold substrate to below 100 ℃ after film coating is stopped, opening the furnace, and taking out the mold substrate.
Tests show that the thickness of the coating on the surface of the die is 2.86 mu m, the hardness is 35.6GPa, the film-substrate binding force reaches 68N, and the friction coefficient is 0.25.
Example two:
the surface to be processed of the die-casting die made of the Y10 material is subjected to polishing treatment, and the die matrix is subjected to oil removal, wax removal, cleaning and drying by adopting an ultrasonic cleaning method.
The cleaned and dried die base body is placed in a cavity of vacuum cathode ion plating equipment, heated to 500 ℃, vacuumized to 5 multiplied by 10 < -3 > Pa, and Ar gas is introduced to maintain the air pressure at 1.2 Pa. Starting an anode layer ion source, wherein the current is 3A, the rotating speed of a substrate frame is 1rpm, the negative bias is-900V, and the bombardment time is 60 min.
After glow cleaning, vacuum adjusting to 0.9Pa, opening a metal Cr target, keeping the bias voltage at-300V and the current at 80A, and depositing for 10min to obtain a Cr metal interface bonding layer with the thickness of 180 nm.
After the Cr bonding layer deposition is finished, the bias voltage is reduced to-150V, and N is introduced2Controlling the air pressure at 0.8Pa, the matrix temperature at 450 ℃, the duty ratio at 80%, the substrate frame rotating speed at 1rpm and the current at 80A, starting to deposit the CrN transition layer, and depositing for 20min to obtain the CrN transition layer with the thickness of 300 nm.
Closing the Cr target, opening the CrAl alloy target, keeping the bias voltage at-150V, controlling the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, the substrate frame rotating speed at 1rpm, and the current at 70A, depositing a CrAlN transition layer for 8min, and the thickness is 150 nm.
And after the deposition of the transition layer is finished, opening a CrV target, a CrAl target and a CrSi target, keeping the bias voltage at-150V, controlling the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, keeping the rotating speed of the substrate frame at 1rpm, keeping the CrV target current at 75A, the CrAl target current at 80A and the CrSi target current at 60A, and depositing for 15min to obtain a CrAlSiN/CrAlVN supporting layer with the thickness of 300 nm.
Continuously introducing 1minC every 5min2H2And keeping the air pressure at 0.8Pa, the matrix temperature at 400 ℃, the duty ratio at 80%, keeping the rotating speed of the substrate frame at 1.5rpm, the CrV target current at 75A, the CrAl target current at 80A and the CrSi target current at 60A, and depositing for 120min to obtain a CrAlSiCN/CrAlVCN functional layer with the thickness of 3 mu m. And (4) turning off all target power supplies, stopping all gas, cooling the mold substrate to below 100 ℃ after film coating is stopped, opening the furnace, and taking out the mold substrate.
Tests show that the thickness of the coating on the surface of the die is 3.13 mu m, the hardness is 35.2GPa, the film-substrate binding force reaches 70N, and the friction coefficient is 0.28.
The composite coating provided by the invention has the advantages of good self-lubricating property, high hardness and strength, relatively large interlayer bonding force, good mechanical property and structural stability.
The composite coating for the die-casting die and the deposition method thereof provided by the invention have the advantages that the composite metal carbonitride coating with the gradient structure has high compactness and extremely high hardness and chemical stability, and the surface hardness, the wear resistance, the high temperature resistance and the corrosion resistance of the die-casting die can be obviously improved. The high hardness of the coating structure can ensure that the die can effectively resist the impact of molten metal; the high temperature resistance can protect the die and avoid the early cracking and deformation of the die due to thermal fatigue; corrosion resistance, and the mould can be protected from corrosion failure; meanwhile, the good self-lubricating property of the amorphous carbon helps the mold to demould smoothly, and damage to the surface of the product is avoided.
Although the embodiments of the present invention have been described above, the embodiments are only given as examples and are not intended to limit the scope of the present invention. These new embodiments can be implemented in other various ways, and various omissions, substitutions, and changes can be made without departing from the spirit of the present invention. These embodiments and modifications thereof are included in the scope and gist of the present invention, and are also included in the invention described in the claims and the equivalent scope thereof.
Claims (5)
1. The method is characterized in that the composite coating for the die-casting die is adopted, and the composite coating consists of a bonding layer, a transition layer, a supporting layer and a functional layer which are sequentially stacked from inside to outside and deposited on a die matrix;
the bonding layer is a Cr bonding layer for improving the bonding force between the composite coating and the surface of the die;
the transition layer is formed by compounding a CrN transition layer and a CrAlN transition layer, and the CrN transition layer is positioned between the Cr bonding layer and the CrAlN transition layer;
the supporting layer is of a multilayer structure formed by alternately overlapping and compounding CrAlSiN layers and CrAlVN layers, and the CrAlVN layers are positioned on the CrAlN transition layers and alternately overlapped with the CrAlSiN layers;
the functional layer is of a multilayer structure formed by alternately overlapping and compounding CrAlSiCN layers and CrAlVCN layers, and the CrAlVCN layers are positioned on the CrAlSiN layers on the outermost layers and are alternately overlapped with the CrAlSiCN layers;
in the CrAlN layer, the atomic percent of Al is 20-40 at.%;
the thickness of the CrN layer is 200-400nm, and the thickness of the CrAlN layer is 100-200 nm;
the atomic percent of Si in the CrAlSiN layer of a single layer in the supporting layer is 5-10at.%, and the atomic percent of Al in the CrAlSiN layer is 20-30 at.%; the atomic percent of V in the CrAlVN layer of the monolayer is 7-12at.%, and the atomic percent of Al is 20-30 at.%;
in one period of the supporting layer, the thickness of the CrAlVN layer is 20-40nm, the thickness of the CrAlSiN layer is 10-20nm, and the total thickness of the supporting layer is 300-600 nm;
in the functional layer, the CrAlSiCN layer and the CrAlVCN layer are respectively made of (CrAl, CrV) N nanocrystals embedded in amorphous Si3N4And a crystal structure in which amorphous C atoms are doped in the gap;
the functional layer comprises the following layers in atomic percentage: 15-30 at.% Cr, 10-20 at.% Al, 7-12at.% V, 5-10at.% Si, 3-5 at.% C, 40-49 at.% N;
the thickness of the functional layer is 2-3 μm;
the thickness of the Cr bonding layer is 100-200 nm;
the deposition method comprises the following steps:
1) glow cleaning, namely putting the pretreated mould substrate into vacuum cathode arc ion plating equipment, vacuumizing and heating until the surface temperature of the substrate reaches 300-500 ℃, controlling the air pressure to be 1.0-1.5Pa, and filling Ar gas for glow discharge cleaning;
2) preparing a Cr layer, adjusting the vacuum pressure to 1/2-2/3 of the pressure in glow cleaning, starting a metal Cr target position, and depositing a Cr bonding layer;
3) preparing CrN transition layer, reducing bias voltage, and introducing N2The mixed gas with Ar is controlled to have the pressure of 0.5-1.2Pa, the substrate temperature is 300-;
4) preparing a CrAlN transition layer, closing a metal Cr target position, opening a CrAl alloy target position, keeping bias voltage unchanged, and introducing N2Maintaining the air pressure at 0.5-1.2Pa, the matrix temperature at 300-500 ℃, and depositing a CrAlN transition layer;
5) preparing a supporting layer, simultaneously opening CrAl, CrV and CrSi target positions, and introducing N2Keeping the air pressure at 0.8-3.0Pa and the matrix temperature at 300-;
6) preparing a functional layer, keeping the target positions of CrAl, CrV and CrSi open, and introducing Ar and N2Intermittently introducing C while introducing the mixed gas2H2The vacuum degree is kept at 0.8-3.0Pa, the matrix temperature is 300-.
2. The method of claim 1,
in the step 1), when glow discharge cleaning is carried out, starting the anode layer ion source voltage at 500-600V, the current at 3-5A, the rotating speed of the substrate frame at 1-3rpm, the negative bias at-900V and the bombardment time at 60-80 min;
and/or the presence of a gas in the gas,
in the step 2), starting a metal Cr target position, controlling the current to be 60-90A, controlling the negative bias voltage to be-300V, and depositing for 2-10 min.
3. The method of claim 1,
in the step 3) and the step 4), the rotating speed of the substrate frame is kept at 1-3rpm, the current is controlled at 70-100A, and the duty ratio is 60-80%;
the deposition time of the CrN transition layer is 20-30min, and the deposition time of the CrAlN transition layer is 10-20 min.
4. The method of claim 1,
in the step 5), the output current of each target is controlled to be 70-100A, the negative bias voltage is 60-120V, and the duty ratio is 50-80%;
during alternate deposition, the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target and 2-3rpm when passing through a CrSi target, and the deposition time is 30-60min totally.
5. The method of claim 1,
in the step 6), the output current of each target is controlled to be 70-100A, and Ar gas and N are introduced every time2Introducing 1minC at the same time when the mixed gas is 4min2H2(ii) a Controlling the negative bias voltage to be 60-120V and the duty ratio to be 50-80%;
during alternate deposition, the rotating speed is 1-1.5rpm when passing through a CrAl target, 1.5-2rpm when passing through a CrV target and 1.5-2rpm when passing through a CrSi target, and the deposition time is 80-120min totally.
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