CN107326360B - Nano multilayer gradient composite anti-erosion coating structure and preparation method thereof - Google Patents

Nano multilayer gradient composite anti-erosion coating structure and preparation method thereof Download PDF

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CN107326360B
CN107326360B CN201710572249.3A CN201710572249A CN107326360B CN 107326360 B CN107326360 B CN 107326360B CN 201710572249 A CN201710572249 A CN 201710572249A CN 107326360 B CN107326360 B CN 107326360B
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tin
nitriding
coating
substrate
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CN107326360A (en
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张虹虹
何卫锋
何光宇
聂祥樊
李应红
廖斌
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Xian Jiaotong University
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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
    • 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
    • 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
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—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
    • 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
    • C23C14/48—Ion implantation
    • 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
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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

Abstract

The invention discloses an erosion-resistant coating structure compounded by nanometer multilayer gradients, which sequentially comprises a nitriding layer, an embedded combination layer and a structure formed by circularly superposing a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nanometer multilayer from a substrate to the surface of the coating. In addition, the invention discloses a preparation method of the coating structure, which comprises the following steps: by surface nitriding, the material properties of the surface and the subsurface of the matrix are similar to those of a coating material, so that the stress concentration phenomenon at the film-substrate junction is relieved; performing ion implantation on the nitrided substrate surface by adopting a metal vacuum steam ion source implantation method to form an embedded bonding layer; on the bonding layer, by continuously controlling N input by magnetic filtration vacuum cathode arc deposition method2Flow rate, depositing a periodic cycle structure consisting of a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nano multilayer in sequence. The nano-gradient multilayer composite coating structure has high hardness, high toughness and excellent film-substrate binding force, thereby having good erosion resistance.

Description

Nano multilayer gradient composite anti-erosion coating structure and preparation method thereof
Technical Field
The invention relates to the technical field of material surface modification, in particular to an anti-erosion composite coating structure which integrates a nitriding structure, an ion injection structure, a nano multilayer structure and a gradient structure and has high film-substrate binding force and high toughness; and a coating preparation method which is correspondingly and effectively combined with a plurality of surface strengthening treatment technologies such as surface nitriding, ion implantation, magnetic filtration vacuum cathode arc plasma deposition and the like.
Background
Helicopter land navigation, sea navigation and airborne troops in China carry out important equipment which is indispensable for diversified combat tasks such as ground attack, firepower suppression, logistics transportation and the like in complex ground environments, a fixed field or a special airport is often not available for combat, and a used take-off and landing field is usually very simple and even temporary sandy land, land or grassland. When the helicopter takes off and lands and flies at low altitude in a sand-dust environment, the sand-dust particles on the ground are mixed with air by rotor wing downwash airflow, the air flow is sucked by an engine, and the sand-dust particles are brought into the air flow at high speed, the sucked sand-dust firstly passes through the air compressor to cause erosion abrasion to the rotor blades of the air compressor moving at high speed, so that the blades have the problems of increased surface roughness, bent front edge, shortened chord length, reduced thickness and the like, the supercharging ratio, the efficiency and the circulation capacity of the air compressor are reduced, the overall parameters of the engine are further attenuated, and the comprehensive operational performance of the engine is influenced; under severe conditions, sand erosion also causes structural damage such as pits, bulges, gaps, cracks and the like on the surface of the blade, the structural integrity of the blade is damaged, the natural vibration frequency of the blade is changed, the fatigue strength of the blade is reduced, and the reliability and the safety of an engine are seriously threatened.
According to statistics, the sand dust environment accounts for more than 50% of the total area of China, and mainly comprises fine sand in the northwest tacrama dry region, large-area coarse sand in the southwest region, sand beach in the southeast coastal region and the like. The problem of anti-terrorism and stability maintenance exists throughout the year in the northwest region, local conflict often occurs in the southwest region, the social stability is disturbed, and the southeast region needs to be prepared for anti-splitting all the time to maintain the national ownership. Therefore, from the perspective of national economy and national defense safety, how to improve the problem of sand erosion resistance of the compressor blade of the helicopter engine is extremely important and urgent.
The coating is an effective measure for improving the sand erosion resistance of the aero-engine compressor blade. In the early research period, the hardness of the coating is considered as the key for improving the erosion resistance of the coating, and in order to improve the sand erosion resistance of the compressor blade, the army has also prepared a TiN ceramic coating with high hardness on the surface of the blade, however, in the gulf war and the Afghanistan war, the compressor blade with the ceramic coating with high hardness is still found to be seriously damaged. Therefore, the single-layer coating with simple structure and single performance can not meet the sand dust protection requirement of the aero-engine compressor blade. Thus, a ceramic/metal multilayer coating in which a metal material is added to a high-hardness ceramic coating and ceramic layers and metal layers are alternately arranged is produced. Research shows that compared with a single-layer structure, the hardness of the coating is reduced by adding the metal layer, the overall toughness of the coating is improved to a certain extent, however, a large number of interlayer interfaces exist in the traditional multilayer structure, and due to the fact that the material properties of two sides of the interfaces are different, stress concentration is easily caused, interlayer cracks are further generated, and finally the coating is peeled off. In order to solve the problem of stress concentration caused by different material properties at two sides of an interlayer interface in a multilayer coating structure, a gradient coating becomes a research hotspot of scholars. The coating structure is characterized in that in the coating deposition process, the flow of input gas is continuously controlled in real time, so that a special gradient structure is generated between a metal layer and a ceramic layer, an interlayer interface with abrupt material properties does not exist any more, and the problem of stress concentration of the interlayer interface can be effectively solved. With the development of nano science and technology, due to the specific 'super-hard effect' and superior mechanical properties of the nano structure, the nano coating becomes an important development direction of hard coating materials.
Besides the structural characteristics of the coating, the bonding force between the coating and the substrate is also an important influence factor influencing the erosion resistance of the coating. At present, most scholars add a layer of metal Ti with transition effect between a TiN ceramic layer and a substrate to improve the coating bonding force, although the mode is helpful to release the internal stress between the ceramic layer and the substrate and can improve the film-substrate bonding force to a certain extent, the film-substrate bonding force still can not meet the requirement of sand erosion resistance because an obvious interlayer interface still exists between the Ti layer and the substrate. The nitriding technology can carry out surface modification treatment on the matrix, so that the material properties of the surface of the matrix and the subsurface of the matrix are similar to those of a coating material, the stress concentration phenomenon at the film-substrate junction is relieved, and a foundation is laid for improving the film-substrate binding force. In addition, ion implantation is a unique surface modification technique, which is characterized in that selected elements are ionized into charged ions in a vacuum container, and the charged ions are accelerated by tens of thousands or even hundreds of thousands of volts to become energy-carrying ions which are implanted into a substrate subsurface layer to form an embedded bonding layer, and the structure can effectively and tightly connect the substrate and the coating together to obtain ultrahigh film-substrate bonding force.
Disclosure of Invention
In view of the above technical background, one of the objects of the present invention is to combine the advantages of nitriding structure, ion implantation structure, nano multilayer structure and gradient structure to provide an erosion-resistant nano multilayer gradient composite coating structure with high film-based bonding force and high toughness; meanwhile, a method for preparing the nano multilayer gradient composite anti-erosion coating is provided by effectively combining various surface strengthening treatment technologies such as surface nitriding, ion implantation, magnetic filtration vacuum cathode arc deposition, magnetic filtration vacuum cathode arc sputtering and the like. The specific invention content is as follows:
1. the coating structure comprises a nitriding structure, an embedded bonding layer, a nano multilayer structure and a gradient structure. A nitriding layer, an ion injection layer and a repeated structure formed by sequentially and circularly superposing a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nano multilayer structure are sequentially laminated from the substrate to the surface of the coating, and the three layers form a nano multilayer gradient composite anti-erosion coating structure; the repeated structure is repeatedly and circularly laminated for n times, and the value range of n is a positive integer larger than 0.
2. The depth of the surface nitriding layer is 20-50 um; the embedded bonding layer has an implantation depth of 60-200 nm. The preferable range is 100-160 nm.
3. In one or more repeated structures of the composite coating structure, the thickness ratio of the metal Ti layer, the Ti → TiN gradient layer and the TiN/Ti nano multilayer structure is 1: 0.5-3: 0.5-9;
4. in the TiN/Ti nano multilayer structure, the thickness of the Ti layer and the TiN layer is more than 10nm and not more than 100nm, and the thickness ratio is 1: 0.5-9;
5. the total thickness of the composite coating structure is 18-24 um;
6. in the composite coating structure, a repeated structure consisting of a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nano multilayer which are sequentially and circularly superposed is circularly superposed for n times, and the value range of n is a positive integer which is more than 0 and less than or equal to 10.
7. The matrix is one or more of stainless steel, TC11 and TC 4.
8. Combining surface nitriding, metal vacuum steam ion source injection, magnetic filtration vacuum cathode arc deposition, magnetic filtration vacuum cathode arc sputtering and a plurality of techniques capable of compiling a flow controller, wherein the surface nitriding technique can enable the material properties of the surface and the subsurface of the substrate to be similar to those of a coating material so as to relieve the stress concentration phenomenon at the film-substrate interface; the metal vacuum steam ion source injection method is used for carrying out ion injection on the surface of the nitrided substrate to form an embedded bonding layer; combining a magnetic filtration vacuum cathode arc deposition method and a flow controller capable of being compiled, and sequentially preparing a Ti metal layer, a Ti → TiN gradient layer, a TiN ceramic layer and a TiN/Ti nano multilayer structure by continuously controlling the input N2 flow; the magnetic filtering vacuum cathode arc sputtering technology is used for avoiding the influence of excessive internal stress formed inside the coating on the comprehensive performance of the coating.
9. The specific preparation method of each layer structure comprises the following steps of performing surface nitriding treatment on a matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3The glow voltage is 700-1000V, the current is 12-15A, the vacuum degree in the furnace is 100-150 Pa, the nitriding temperature is 300 ℃, and the nitriding time is 1-4 h; .
1) The specific preparation method of each layer structure comprises the following steps of performing surface nitriding treatment on a matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3The glow voltage is 700-1000V, the current is 12-15A, the vacuum degree in the furnace is 100-150 Pa, the nitriding temperature is 300 ℃, and the nitriding time is 1-4 h; 2) preparing ion implantation combined layer by metal vacuum vapor ion source implantation method with vacuum degree of 1.0 × 10-4～1.0×10-3Pa, the injection voltage is 8-15 kV, the beam intensity is 4-8 mA, and the total dose of injected ions is 1.0 multiplied by 1015～1.0×1016/cm-2；
3) Preparing a Ti metal layer by adopting a magnetic filtration vacuum cathode arc deposition method, and utilizing a 90-degree magnetic filtration bent pipe, wherein the magnetic field current is 2-4A, and the vacuum degree is 1.0 multiplied by 10-4～1.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, and the beam intensity is 700-800 mA;
4) combining a magnetic filtration vacuum cathodic arc deposition method and a compilable flow controller by continuously controlling the input N2Flow rate, preparing Ti → TiN gradient structure, using 90 deg. magnetic filtering bent tube, vacuum degree is 1.0X 10-4～5.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, the beam intensity is 700-800 mA, N2The flow rate is determined by a proportional function (y is kt, k is more than 0) and a quadratic function (increasing part y is at2A > 0) or a sine function (increasing part y-nsin 2 pi ft, n-20 to 32,
Figure GFW0000021099910000031
) Gradually increasing from 0sccm to 20-32 sccm, preferably with a flow rate of 26 sccm;
5) combining a magnetic filtration vacuum cathodic arc deposition method and a compilable flow controller by controlling N2The flow rate is rapidly switched cyclically between a flow rate (20-32 sccm) and 0 sccm. Preparing a TiN/Ti nano multilayer structure, which is characterized in that: using a 90-degree magnetic filtering bent pipe, the vacuum degree is 1.0 multiplied by 10-4～5.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, and the beam intensity is 700-800 mA;
6) in the preparation process, in order to avoid the influence of overlarge internal stress formed inside the coating on the erosion resistance of the coating, in the preparation process except surface nitriding and ion implantation, a method of magnetic filtration cathode vacuum arc sputtering is adopted, Ti sputtering is carried out every 30-40 minutes, and N during sputtering2The flow is 0sccm, the arcing current is 110-120A, the negative bias is-800V, -600V and-400V in sequence, the duty ratio is 85% -90%, and each negative bias is kept for 30-40 s.
10. And (2) carrying out coarse grinding and fine grinding on the TC4 matrix test sample by using 400-600, 800-1000, 1200 and 2000-mesh sandpaper in sequence until no obvious transverse and longitudinal grinding marks exist, and then polishing the sample after fine grinding by using polishing flannelette and diamond polishing paste until the surface roughness of the sample reaches Ra of 0.02 +/-0.005 mu m.
The polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone sequentially and ultrasonically for 2 times, 10 minutes each time, before being clamped and coated, and is quickly dried by high-purity nitrogen.
Compared with the prior art, the invention has the following advantages:
1. compared with the traditional single multilayer structure, gradient structure or nano structure, the nano multilayer gradient composite anti-erosion coating structure provided by the invention has the advantages of various coating structures and combines the characteristics of various surface strengthening treatment technologies, and provides a composite coating structure integrating a nitriding structure, an ion implantation structure, a nano multilayer structure and a gradient structure. The coating structure not only has high film-substrate binding force and the superhard characteristic of a nano multilayer structure, but also solves the problem of stress concentration caused by different material properties at two sides of an interlayer interface in the multilayer structure due to the addition of a gradient structure, has good impact toughness, is particularly suitable for being deposited on a compressor blade of a helicopter engine to resist the high-speed erosion of sand dust particles, and has great application value.
2. Compared with the traditional PVD (physical vapor deposition) deposition methods such as magnetron sputtering, ion plating and the like, the preparation method provided by the embodiment of the invention effectively combines a plurality of surface strengthening treatment technologies such as surface nitriding, ion implantation, magnetic filtration vacuum cathode arc plasma deposition and the like, wherein the material properties of the surface of a matrix and the subsurface of the matrix are similar to those of a coating material due to the surface nitriding, so that the stress concentration phenomenon at the film-substrate junction is relieved, and a foundation is laid for improving the film-substrate bonding force; the ion implantation technology makes the sub-surface of the substrate exist in the mixed way with the implanted ions forming metal-substrate atoms without a strengthened bonding layer of an interface by implanting the energy-carrying ions into the sub-surface of the substrate, and the 'embedded bonding layer' can effectively and tightly connect the substrate and the coating together to obtain ultrahigh film-substrate binding force. And the existence of the magnetic filtering bent pipe can filter almost all neutral particles, liquid drops, large particles and the like, and is favorable for improving the compactness, the purity, the surface roughness and the like of the film layer.
3. The invention provides that Ti sputtering is carried out every 40 minutes in the film deposition process, the addition of the process can partially release the internal stress in the deposited film on one hand, and on the other hand, because the negative bias of the matrix is set to be very high (sequentially-800V, -600V and-400V) in the sputtering process, titanium ions are rapidly accelerated and impact the surface of the matrix, so that the temperature of the matrix is increased, the generation of the internal stress in the subsequent deposition process is reduced, and the overall toughness and the erosion resistance of the composite coating are improved.
Drawings
FIG. 1 is a schematic representation of the coating structure of the present invention;
FIG. 2 is a comparison of the film-based bond strength of the coating provided in example 3 of the present invention with a conventional multilayer coating (comparative example 1). Wherein (a) is a scratch method acoustic emission signal of a certain traditional multilayer coating, and (b) is a scratch method acoustic emission signal of the coating provided in the embodiment 3 of the present invention, and the comparison of acoustic emission signals of two coatings tested by the scratch method shows that the film-based bonding force of the traditional coating is about 58N, while the film-based bonding force of the coating prepared in the embodiment of the present invention can reach 95N, which is about 70% higher than that of the traditional multilayer coating.
FIG. 3 is a comparison of Rockwell indentation patterns of a coating provided by an embodiment of the present invention and a conventional multi-layer coating, wherein (a) the graph shows the Rockwell indentation pattern of the conventional coating (comparative example 1), and (b) the graph shows the Rockwell indentation pattern of a coating provided by the present invention, and the Rockwell indentation pattern of two coatings is compared, and the length and number of cracks around the indentation are counted, so that under the same loading condition, the conventional multi-layer coating has obvious brittle flaking phenomenon around the indentation, and the length and number of cracks around the indentation are also obviously more than those of the coating provided by the present invention (example 1), so that the toughness of the coating provided by the present invention is far better than that of the conventional multi-layer coating.
FIG. 4 is a comparison of nano-and microhardness values for various examples of the present invention. It can be seen from the figure that the coating examples (examples 1-3) proposed by the present invention have higher nano-hardness and microhardness values than the conventional multi-layer coating (comparative example 1), which is improved by about 60%.
FIG. 5 is a graph comparing the average particle loss rate of the sand erosion process of the examples of the present invention. It can be seen from the figure that the mass loss rate of the coating examples (examples 1 to 3) provided by the invention is reduced by about 90% compared with that of the conventional multilayer coating (comparative example 1), and the coating examples have very high erosion resistance.
Detailed Description
The following will describe in detail several embodiments (examples 1 to 3) of the high erosion resistance gradient multilayer composite coating structure and the preparation method thereof according to the present invention, and a preparation embodiment (comparative example 1) of a conventional multilayer coating, specifically including the following steps:
example 1:
1) polishing and cleaning of substrates
And (2) carrying out coarse grinding and fine grinding on the TC4 matrix test sample by using 400-600, 800-1000, 1200 and 2000-mesh sandpaper in sequence until no obvious transverse and longitudinal grinding marks exist, and then polishing the sample after fine grinding by using polishing flannelette and diamond polishing paste until the surface roughness of the sample reaches Ra of 0.02 +/-0.005 mu m.
The polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone sequentially and ultrasonically for 2 times, 10 minutes each time, before being clamped and coated, and is quickly dried by high-purity nitrogen.
2) Surface nitriding treatment
The surface nitriding treatment process of the matrix is as follows: performing surface nitriding treatment on the matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3The glow voltage is 800V, the current is 13A, the vacuum degree in the furnace is 100Pa, the nitriding temperature is 400 ℃, and the nitriding time is 1 h.
3) Preparation of an "Embedded bonding layer
The preparation of the embedded bonding layer on the surface and the subsurface of the substrate comprises three steps:
firstly, a certain amount of Ti element is pre-injected to the surface of a nitrided substrate by utilizing a metal vacuum vapor ion source (MEVVA), the pre-injection voltage is 8.2kV, the beam current is 5A, and the injection dosage is 5.6 multiplied by 1014/cm2(ii) a Then closing the metal vacuum vapor ion source, depositing a layer of nano metal Ti on the surface of the substrate by using a magnetic filtration vacuum arc deposition system (FCVA), wherein the bias voltage of the substrate for depositing the nano Ti layer is-200V, the duty ratio is 90%, the arcing current is 100mA, the current of a magnetic filtration electric field is 2.0A, the voltage is 24.2V, and the deposition time is 10 s; finally, increasing the injection voltage by using a metal vacuum vapor ion source (MEVVA), injecting a large amount of Ti element into the nano Ti layer and the base material to finally form an embedded bonding layer for improving the film-base bonding force, wherein the injection voltage of Ti ions is 12kV, the beam current is 5.8mA, and the injection dose is 8.2 multiplied by 1014/cm2。
4) Metal transition Ti layer deposition
The deposition of the metal Ti transition layer is carried out on the embedded bonding layer by utilizing a magnetic filtration vacuum arc deposition (FCVA) system, and the specific process parameters are as follows: magnetic filtering current: 2.0A, voltage: 24.2V, vacuum degree 8.0X 10-4Pa, the arcing current is 100A, the negative bias is-200V, the duty ratio is 90%, the beam intensity is 700mA, and the deposition time is 30 min;
5) ti → TiN gradient structure deposition
The magnetic filtration vacuum arc deposition (FCVA) system is utilized to continuously control the input N2 flow in real time through a compilable flow controller, and a gradient structure gradually changed from metal Ti to ceramic TiN is deposited on the metal transition layer. The specific process parameters are as follows: vacuum degree of 8.0X 10-4～5.0×10-3Pa, arc starting current of 100A, negative bias of 200V, duty ratio of 90%, beam intensity of 700mA, and N2The flow rate was gradually increased from 0sccm to 26sccm as a proportional function y of 0.007t (t represents deposition time) for a deposition period of 60 min.
6) Deposition of TiN/Ti nano-multilayer structures
Input of N by compilable flow controller using magnetic filtration vacuum arc deposition (FCVA) system2The flow rate realizes step-type cyclic switching between the two flow rates of 26sccm and 0sccm, and the specific process parameters are as follows: vacuum degree of 1.0X 10-4～5.0×10-3Pa, the arcing current is 100A, the negative bias is 200V, the duty ratio is 90%, the beam intensity is 700-800 mA, the deposition time of each nano Ti layer is 12s, the deposition time of each nano TiN layer is 48s, and the total deposition time of the TiN/Ti nano multilayer structure is 90 min.
In addition, in the deposition of other film layers except for surface nitriding and ion implantation, Ti ion sputtering was performed every 40 minutes of deposition. The process can release the internal stress in the deposited film layer on one hand, and on the other hand, the Ti ions impact the substrate at high speed, so that the temperature of the substrate can be increased, the generation of subsequent internal stress is reduced, and the mechanical properties such as the integral toughness of the film layer and the like are improved. The specific process parameters are as follows: arcing current: 110mA, magnetic filter current: 2.0A, voltage: 24.2V, the substrate bias was adjusted to-800V, -600V and-400V in this order, and sputtering was carried out for 30s at each bias.
Example 2:
1) polishing and cleaning of substrates
And (3) carrying out coarse grinding and fine grinding on the TC4 matrix test sample by using 400-600, 800-1000, 1200 and 2000-mesh sandpaper in sequence, and then polishing the sample after fine grinding by using polishing flannelette and diamond polishing paste until the surface roughness of the sample reaches Ra of 0.02 +/-0.005 mu m.
The polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone for 10 minutes in sequence before being clamped and coated with a film, and is quickly dried by high-purity nitrogen.
2) Surface nitriding treatment
The surface nitriding treatment process of the matrix is as follows: performing surface nitriding treatment on the matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3The glow voltage is 800V, the current is 13A, the vacuum degree in the furnace is 100Pa, the nitriding temperature is 400 ℃, and the nitriding time is 1 h.
3) Preparation of an "Embedded bonding layer
The preparation of the embedded bonding layer on the surface and the subsurface of the substrate comprises three steps:
firstly, a certain amount of Ti element is pre-injected to the surface of a nitrided substrate by utilizing a metal vacuum vapor ion source (MEVVA), the pre-injection voltage is 8.2kV, the beam current is 5A, and the injection dosage is 5.6 multiplied by 1014/cm2(ii) a Then closing the metal vacuum vapor ion source, depositing a layer of nano metal Ti on the surface of the substrate by using a magnetic filtration vacuum arc deposition system (FCVA), wherein the bias voltage of the substrate for depositing the nano Ti layer is-200V, the duty ratio is 90%, the arcing current is 100mA, the current of a magnetic filtration electric field is 2.0A, the voltage is 24.2V, and the deposition time is 10 s; finally, increasing the injection voltage by using a metal vacuum vapor ion source (MEVVA), injecting a large amount of Ti element into the nano Ti layer and the base material to finally form an embedded bonding layer for improving the film-base bonding force, wherein the injection voltage of Ti ions is 12kV, the beam current is 5.8mA, and the injection dose is 8.2 multiplied by 1014/cm2。
4) Metal transition Ti layer deposition
The deposition of the metal Ti transition layer is carried out on the embedded bonding layer by utilizing a magnetic filtration vacuum arc deposition (FCVA) system, and the specific process parameters are as follows: magnetic filtering current: 2.0A, voltage: 24.2V, vacuum degree 8.0X 10-4Pa, the arcing current is 100A, the negative bias is-200V, the duty ratio is 90%, the beam intensity is 700mA, and the deposition time is 15 min;
5) ti → TiN gradient structure deposition
Input of N by compilable flow controller using magnetic filtration vacuum arc deposition (FCVA) system2The flow is continuously controlled in real time, and a gradient structure gradually changed from metal Ti to ceramic TiN is deposited on the metal transition layer. The specific process parameters are as follows: vacuum degree of 8.0X 10-4～5.0×10-3Pa, arc starting current of 100A, negative bias of 200V, duty ratio of 90%, beam intensity of 700mA, and N2The flow rate was gradually increased from 0sccm to 26sccm as a proportional function y of 0.0144t (t represents deposition time) for a deposition period of 30 min.
6) Deposition of TiN/Ti nano-multilayer structures
Using a magnetic filtration vacuum arc deposition (FCVA) system, by means of braidingInterpreting flow controller, for input N2The flow rate realizes step-type cyclic switching between the two flow rates of 26sccm and 0sccm, and the specific process parameters are as follows: vacuum degree of 1.0X 10-4～5.0×10-3Pa, the arcing current is 100A, the negative bias is 200V, the duty ratio is 90%, the beam intensity is 700-800 mA, the deposition time of each nano Ti layer is 12s, the deposition time of each nano TiN layer is 48s, and the total deposition time of the TiN/Ti nano multilayer structure is 45 min.
7) Cyclic superposition of modulation periods
And (4) circularly operating the processes in the steps (4) to (6) for 2 times.
In addition, in the deposition of other film layers except for surface nitriding and ion implantation, Ti ion sputtering was performed every 40 minutes of deposition. The process can release the internal stress in the deposited film layer on one hand, and on the other hand, the Ti ions impact the substrate at high speed, so that the temperature of the substrate can be increased, the generation of subsequent internal stress is reduced, and the mechanical properties such as the integral toughness of the film layer and the like are improved. The specific process parameters are as follows: arcing current: 110mA, magnetic filter current: 2.0A, voltage: 24.2V, the substrate bias was adjusted to-800V, -600V and-400V in this order, and sputtering was carried out for 30s at each bias.
Example 3:
1) polishing and cleaning of substrates
And (3) carrying out coarse grinding and fine grinding on the TC4 matrix test sample by using 400-600, 800-1000, 1200 and 2000-mesh sandpaper in sequence, and then polishing the sample after fine grinding by using polishing flannelette and diamond polishing paste until the surface roughness of the sample reaches Ra of 0.02 +/-0.005 mu m.
The polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone for 10 minutes in sequence before being clamped and coated with a film, and is quickly dried by high-purity nitrogen.
2) Surface nitriding treatment
The surface nitriding treatment process of the matrix is as follows: performing surface nitriding treatment on the matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3Glow voltage is 800V, current is 13A, vacuum degree in the furnace is 100Pa, nitriding temperature is 4Nitriding time is 1h at 00 ℃.
3) Preparation of an "Embedded bonding layer
The preparation of the embedded bonding layer on the surface and the subsurface of the substrate comprises three steps:
firstly, a certain amount of Ti element is pre-injected to the surface of a nitrided substrate by utilizing a metal vacuum vapor ion source (MEVVA), the pre-injection voltage is 8.2kV, the beam current is 5A, and the injection dosage is 5.6 multiplied by 1014/cm2(ii) a Then closing the metal vacuum vapor ion source, depositing a layer of nano metal Ti on the surface of the substrate by using a magnetic filtration vacuum arc deposition system (FCVA), wherein the bias voltage of the substrate for depositing the nano Ti layer is-200V, the duty ratio is 90%, the arcing current is 100mA, the current of a magnetic filtration electric field is 2.0A, the voltage is 24.2V, and the deposition time is 10 s; finally, increasing the injection voltage by using a metal vacuum vapor ion source (MEVVA), injecting a large amount of Ti element into the nano Ti layer and the base material to finally form an embedded bonding layer for improving the film-base bonding force, wherein the injection voltage of Ti ions is 12kV, the beam current is 5.8mA, and the injection dose is 8.2 multiplied by 1014/cm2。
4) Metal transition Ti layer deposition
The deposition of the metal Ti transition layer is carried out on the embedded bonding layer by utilizing a magnetic filtration vacuum arc deposition (FCVA) system, and the specific process parameters are as follows: magnetic filtering current: 2.0A, voltage: 24.2V, vacuum degree 8.0X 10-4Pa, the arcing current is 100A, the negative bias is-200V, the duty ratio is 90%, the beam intensity is 700mA, and the deposition time is 10 min;
5) ti → TiN gradient structure deposition
Input of N by compilable flow controller using magnetic filtration vacuum arc deposition (FCVA) system2The flow is continuously controlled in real time, and a gradient structure gradually changed from metal Ti to ceramic TiN is deposited on the metal transition layer. The specific process parameters are as follows: vacuum degree of 8.0X 10-4～5.0×10-3Pa, arc starting current of 100A, negative bias of 200V, duty ratio of 90%, beam intensity of 700mA, and N2The flow rate was gradually changed from 0sccm as a proportional function y of 0.0144t (t represents deposition time)Increment to 26sccm for a deposition period of 20 min.
6) Deposition of TiN/Ti nano-multilayer structures
Input of N by compilable flow controller using magnetic filtration vacuum arc deposition (FCVA) system2The flow rate realizes step-type cyclic switching between the two flow rates of 26sccm and 0sccm, and the specific process parameters are as follows: vacuum degree of 1.0X 10-4～5.0×10-3Pa, the arcing current is 100A, the negative bias is 200V, the duty ratio is 90%, the beam intensity is 700-800 mA, the deposition time of each nano Ti layer is 12s, the deposition time of each nano TiN layer is 48s, and the total deposition time of the TiN/Ti nano multilayer structure is 30 min.
7) Cyclic superposition of modulation periods
And (4) performing the process in the steps (4) to (6) for 4 times in a total circulation mode.
In addition, in the deposition of other film layers except for surface nitriding and ion implantation, Ti ion sputtering was performed every 40 minutes of deposition. The process can release the internal stress in the deposited film layer on one hand, and on the other hand, the Ti ions impact the substrate at high speed, so that the temperature of the substrate can be increased, the generation of subsequent internal stress is reduced, and the mechanical properties such as the integral toughness of the film layer and the like are improved. The specific process parameters are as follows: arcing current: 110mA, magnetic filter current: 2.0A, voltage: 24.2V, the substrate bias was adjusted to-800V, -600V and-400V in this order, and sputtering was carried out for 30s at each bias.
Comparative example 1 (preparation of some conventional multilayer coating):
1) polishing and cleaning of substrates
And (2) carrying out coarse grinding and fine grinding on the TC4 matrix test sample by using 400-600, 800-1000, 1200 and 2000-mesh sandpaper in sequence until no obvious transverse and longitudinal grinding marks exist, and then polishing the sample after fine grinding by using polishing flannelette and diamond polishing paste until the surface roughness of the sample reaches Ra of 0.02 +/-0.005 mu m.
The polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone sequentially and ultrasonically for 2 times, 10 minutes each time, before being clamped and coated, and is quickly dried by high-purity nitrogen.
2) Metal transition Ti layer deposition
The deposition of the metal Ti transition layer is carried out on the embedded bonding layer by utilizing a magnetic filtration vacuum arc deposition (FCVA) system, and the specific process parameters are as follows: magnetic filtering current: 2.0A, voltage: 24.2V, vacuum degree 8.0X 10-4Pa, the arcing current is 100A, the negative bias is-200V, the duty ratio is 90%, the beam intensity is 700mA, and the deposition time is 10 min;
3) deposition of TiN ceramic layer
A TiN ceramic layer was deposited on the Ti → TiN gradient structure using a magnetic filtered vacuum arc deposition (FCVA) system, with the input N2 flow held constant at 26sccm by a compilable flow controller. The specific process parameters are as follows: vacuum degree of not less than 8X 10-3Pa, substrate bias: -200V, duty cycle: 90%, arcing current: 100mA, magnetic filter current: 2.0A, voltage: 24.2V, the deposition time is 40 min.
4) Cyclic superposition of modulation periods
And (4) performing the process in the steps (4) to (6) for 4 times in a total circulation mode.
It should be noted that, for simplicity of description, the above examples are described as a series of steps according to specific embodiments, but the specific embodiments of the present invention are not considered to be limited thereto. Various modifications and improvements based on the above-described embodiments may be made by those skilled in the art within the spirit and principle of the invention, and these modifications and improvements fall within the scope of the invention. It will be appreciated by those skilled in the art that the embodiments described in the specification are preferred embodiments, that the acts referred to are not necessarily essential to the invention, and that the embodiments and features of the embodiments may be combined without conflict. In addition, the base material selected in the embodiment is TC4 titanium alloy for processing the aero-engine compressor blade, but the base body in the embodiment of the invention is not limited to a TC4 base body, and can also be TC11, stainless steel and other materials commonly used for the aero-engine compressor blade. The scope of the invention is defined by the claims and their equivalents.

Claims (10)

1. A nanometer multilayer gradient composite erosion-resistant coating structure is characterized in that: the coating structure comprises a nitriding structure, an embedded combination layer, a nano multilayer structure and a gradient structure which are integrated, wherein the nitriding layer, an ion injection layer and a repeating structure formed by sequentially and circularly superposing a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nano multilayer structure are sequentially stacked from a substrate to the surface of the coating, and the three layers form the nano multilayer gradient composite anti-erosion coating structure; the repeated structure is repeatedly and circularly laminated for n times, and the value range of n is a positive integer larger than 0.
2. The nanolayered gradient composite impact resistant coating structure of claim 1, wherein: the depth of the surface nitriding layer is 20-50 um; the embedded bonding layer has an implantation depth of 60-200 nm.
3. The nanolayered gradient composite impact resistant coating structure of claim 1, wherein: in the one or more repeating structures, the thickness ratio of the Ti metal layer, the Ti → TiN gradient layer, and the TiN/Ti nano multilayer structure is 1: (0.5-3): (0.5 to 9).
4. The nanolayered gradient composite impact resistant coating structure of claim 1, wherein: in the TiN/Ti nanometer multilayer structure, the thickness of the Ti layer and the TiN layer is more than 10nm and not more than 100nm, and the thickness ratio is 1: (0.5 to 9).
5. The nanolayered gradient composite impact resistant coating structure of claim 1, wherein:
the total thickness of coating structure is 18~24 um.
6. The nanolayered gradient composite impact resistant coating structure of claim 1, wherein: the repeated structure formed by sequentially and circularly superposing a Ti metal layer, a Ti → TiN gradient layer and a TiN/Ti nano multilayer is circularly laminated for n times, and the value range of n is a positive integer which is more than 0 and less than or equal to 10.
7. The gradient multilayer composite coating structure of claim 1, wherein: the matrix is one or more of stainless steel, TC11 and TC 4.
8. The method for preparing a nano multilayer gradient composite erosion-resistant coating structure as claimed in any one of claims 1 to 7, wherein: combining surface nitriding, metal vacuum vapor ion source injection, magnetic filtration vacuum cathode arc deposition, magnetic filtration vacuum cathode arc sputtering and processing of a compilable flow controller; wherein, the surface nitriding treatment can make the material properties of the surface and the subsurface of the substrate similar to those of a coating material so as to relieve the stress concentration phenomenon at the interface of the film and the substrate; the metal vacuum steam ion source injection treatment is used for carrying out ion injection on the nitrided substrate surface to form an embedded bonding layer; combining the magnetic filtration vacuum cathode arc deposition method with a compilable flow controller process by continuously controlling the input N2Flow, sequentially preparing a Ti metal layer, a Ti → TiN gradient layer, a TiN ceramic layer and a TiN/Ti nano multilayer structure; the magnetic filtration vacuum cathode arc sputtering treatment can avoid the influence of overlarge internal stress formed inside the coating on the comprehensive performance of the coating.
9. The method for preparing a nano multilayer gradient composite erosion-resistant coating structure as claimed in claim 8, wherein the specific preparation method of each layer structure comprises the following steps:
1) performing surface nitriding treatment on the matrix by adopting glow plasma nitriding technology, wherein nitriding gas is NH3The glow voltage is 700-1000V, the current is 12-15A, the vacuum degree in the furnace is 100-150 Pa, the nitriding temperature is 300 ℃, and the nitriding time is 1-4 h;
2) the method for preparing the ion implantation bonding layer by adopting the metal vacuum steam ion source implantation method specifically comprises the following steps:
firstly, a certain amount of Ti element is pre-injected to the surface of the nitrided substrate by utilizing a metal vacuum ion source, and the vacuum degree is 1.0 multiplied by 10-4~1.0×10-3Pa, injection voltage of 815kV, and the beam intensity is 4-8 mA; then, depositing a layer of nano-grade metal Ti on the surface of the substrate by using a magnetic filtration vacuum cathode arc deposition system, and finally injecting a large amount of Ti element into the nano-grade Ti layer and the substrate material by using a metal vacuum ion source; wherein the total dose of implanted ions is 1.0 × 1015~1.0×1016ions/cm2；
3) Preparing a Ti metal layer by adopting a magnetic filtration vacuum cathode arc deposition method, and utilizing a 90-degree magnetic filtration bent pipe, wherein the magnetic field current is 2-4A, and the vacuum degree is 1.0 multiplied by 10-4~1.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, and the beam intensity is 700-800 mA;
4) combining a magnetic filtration vacuum cathodic arc deposition method and a compilable flow controller by continuously controlling the input N2Flow rate, preparing Ti → TiN gradient structure, using 90 deg. magnetic filtering bent tube, vacuum degree is 1.0X 10-4~5.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, the beam intensity is 700-800 mA, and N2Flow rate as a proportional function y = kt, k>0. Quadratic function, increasing fraction y = at2, a>0, or a sinusoidal function, increasing part y = nsin2 pi ft, n =20~32, 0<Gradually increasing the form of f from 0sccm to 20-32 sccm;
5) combining a magnetic filtration vacuum cathodic arc deposition method and a compilable flow controller by controlling N2The flow rate is rapidly and circularly switched between 20-32 sccm and 0 sccm; preparing TiN/Ti nano multi-layer structure by using 90-degree magnetic filtering bent tube with vacuum degree of 1.0 x 10-4~5.0×10-3Pa, the arcing current is 100-110A, the negative bias is 200-250V, the duty ratio is 85% -90%, and the beam intensity is 700-800 mA;
6) in the preparation process, in order to avoid the influence of overlarge internal stress formed inside the coating on the erosion resistance of the coating, in the preparation process except surface nitriding and ion implantation, a method of magnetic filtration cathode vacuum arc sputtering is adopted, Ti sputtering is carried out every 30-40 minutes, and N during sputtering2The flow is 0sccm, the arcing current is 110-120A, the negative bias voltage is-800V, -600V and-400V in sequence, the duty ratio is 85% -90%, and each negative bias voltage isKeeping for 30-40 s.
10. The method for preparing a nanolayered gradient composite erosion resistant coating structure of claim 8, wherein: using 400-600, 800-1000, 1200 and 2000-mesh sandpaper to perform coarse grinding and fine grinding on a TC4 matrix test sample until no obvious transverse and longitudinal grinding marks exist, and then using polishing flannelette and diamond polishing paste to perform polishing treatment on the finely ground sample until the surface roughness of the sample reaches Ra =0.02 +/-0.005 mu m;
the polished substrate needs to be cleaned by adopting absolute ethyl alcohol and acetone sequentially and ultrasonically for 2 times, 10 minutes each time, before being clamped and coated, and is quickly dried by high-purity nitrogen.
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