CN115572974B - Composite coating and preparation method thereof - Google Patents

Composite coating and preparation method thereof Download PDF

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Publication number
CN115572974B
CN115572974B CN202211284649.1A CN202211284649A CN115572974B CN 115572974 B CN115572974 B CN 115572974B CN 202211284649 A CN202211284649 A CN 202211284649A CN 115572974 B CN115572974 B CN 115572974B
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coating
tin
substrate
vapor deposition
tic
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CN115572974A (en
Inventor
翁恺
谢楷
徐春成
吴佳梅
刁安娜
杨剑
吴宇庆
马建元
袁皓
王存华
赵腊文
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Shanghai Qiyao Screw Machinery Co ltd
711th Research Institute of CSIC
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Shanghai Qiyao Screw Machinery Co ltd
711th Research Institute of CSIC
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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
    • C23C28/04—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 only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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

Abstract

The invention provides a composite coating and a preparation method thereof, wherein the preparation method comprises the following steps: step one, preparing a first coating on the surface of a substrate by adopting a surface modification process; step two, preparing the first coating into a second coating by adopting the surface modification process; preparing a third coating on the surface of the second coating by adopting the surface modification process to obtain the composite coating; wherein the surface modification process comprises laser cladding, physical vapor deposition, chemical vapor deposition, build-up welding, carburizing treatment and nitriding treatment; the components of the first coating, the second coating and the third coating comprise titanium, chromium, aluminum and carbides and/or nitrides thereof; the substrate comprises iron, copper, titanium, and alloys thereof; the composite coating is prepared by the preparation method. The composite coating prepared by the preparation method provided by the invention has good acid corrosion resistance and erosion resistance.

Description

Composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of composite coatings, in particular to a composite coating and a preparation method thereof.
Background
The rotor of the water-spraying oil-free screw compressor is made of martensitic stainless steel, acid corrosion can occur in the service environment of wet hydrogen sulfide and chlorine ions, and the acid corrosion occurring part of the surface of the rotor can even partially fall off under the continuous flushing effect of water flow, so that the working performance and the service life of the rotor are seriously shortened. The acid corrosion resistance coating is coated on the surface of the spiral surface of the rotor, so that the acid corrosion resistance and erosion resistance of the rotor can be effectively improved, and the service life of the rotor is prolonged. However, most of the coatings on the market are prepared by the same process at present, only the coating process parameters and the coating materials are changed, the inherent defect problems of a single coating process technology are not solved, and the single coating has the problem of single performance and cannot meet the use requirements of complex environments.
Therefore, it is necessary to provide a method for preparing a composite coating with better acid etching resistance and erosion resistance.
Disclosure of Invention
The invention aims to provide a composite coating and a preparation method thereof, so as to obtain the composite coating with good acid corrosion resistance and erosion resistance.
In order to achieve the above purpose, the present invention provides the following technical scheme:
a method of preparing a composite coating, the method comprising the steps of:
step one, preparing a first coating on the surface of a substrate by adopting a surface modification process;
step two, preparing the first coating into a second coating by adopting the surface modification process;
Preparing a third coating on the surface of the second coating by adopting the surface modification process to obtain the composite coating;
Wherein the surface modification process comprises laser cladding, physical vapor deposition, chemical vapor deposition, build-up welding, carburizing treatment and nitriding treatment;
The components of the first coating, the second coating and the third coating comprise titanium, chromium, aluminum and carbides and/or nitrides thereof;
the substrate comprises iron, copper, titanium, and alloys thereof.
In some embodiments of the invention, the substrate in the first step is stainless steel.
In some embodiments of the present invention, the surface modification processes used in the first and third steps are physical vapor deposition, and the surface modification process used in the second step is laser cladding.
In some embodiments of the present invention, the composition of the first coating and the third coating is at least one of TiAlCrN, tiN, and CrN, and the composition of the second coating includes TiN and TiC.
In some embodiments of the invention, the mass ratio of TiN to TiC in the second coating layer is (1-10): 1-10.
In some embodiments of the present invention, in the first step, the substrate is surface-pretreated prior to the first coating layer being prepared by the surface modification process;
In the third step, the second coating is subjected to the surface pretreatment before the third coating is prepared by adopting the surface modification process;
The surface pretreatment comprises grinding and polishing and cleaning.
In some embodiments of the invention, the cleaning comprises:
And cleaning the substrate by adopting a detergent and clear water in sequence, and then respectively carrying out ultrasonic cleaning on the substrate by adopting propanol and absolute ethyl alcohol.
In some embodiments of the present invention, the process parameters used in the laser cladding are: the laser power is 1300W-2500W, the laser scanning speed is 5-20 mm/s, the powder feeding speed is 10 g/min-40 g/min, and the light spot diameter is 1-5 mm.
In some embodiments of the present invention, the process parameters used in the physical vapor deposition are: the DC power is 1200W-2400W, the DC voltage is 320V-425V, the sputtering voltage is 0.3 Pa-0.8 Pa, the coating time is 3-8 h, and the average film thickness is 2-5 mu m.
In some embodiments of the invention, in step one, the first coating layer having at least one of the components TiAlCrN, tiN, crN is prepared on the surface of the substrate by physical vapor deposition;
Step two, preparing TiN, tiC and the first coating into the second coating through laser cladding;
In the third step, the third coating layer with at least one of components TiAlCrN, tiN, crN is prepared on the surface of the second coating layer through physical vapor deposition.
In order to achieve the above purpose, the present invention also provides the following technical solutions:
The composite coating is prepared by adopting the preparation method and comprises the following steps:
a substrate;
a second coating layer formed on the substrate and comprising at least one of TiAlCrN, tiN, crN and TiC;
A third coating layer formed over the second coating layer, including at least one of TiAlCrN, tiN, crN;
wherein the hardness of the third coating is greater than the hardness of the second coating.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. The preparation method of the composite coating provided by the invention has the advantages that the composite coating with good acid corrosion resistance and erosion resistance is prepared, the preparation method is convenient and feasible, and has good operability, and the composite coating can be used for protecting the rotor of the water-spraying oil-free screw compressor so as to improve the acid corrosion resistance and erosion resistance of the rotor.
2. According to the preparation method of the composite coating, the TiAlCrN coating is prepared on the surface of the substrate through a physical vapor deposition process, the TiAlCrN coating and TiN/TiC mixed powder are fused and covered on the surface of the substrate through a laser cladding process to form a layer of composite coating, and then a layer of novel TiAlCrN coating is prepared on the surface of the composite coating through a second physical vapor deposition process, so that the composite coating with a two-layer structure is finally prepared, and has good acid corrosion resistance and erosion resistance, and can be applied to rotor protection of a water-spraying oil-free screw compressor.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of a composite coating provided by the invention;
Fig. 2 is a schematic structural diagram of a composite coating and a substrate in each step of a preparation method for providing a composite coating according to an embodiment of the invention.
The main reference numerals in the drawings of the present specification are explained as follows:
1-a substrate; 2-a first coating; 3-a second coating; 4-third coating.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The technical scheme of the invention provides a composite coating and a preparation method thereof, and the composite coating and the preparation method thereof are respectively described in detail below. It should be noted that the following description order of the embodiments is not intended to limit the preferred order of the embodiments of the present invention. In the following embodiments, the descriptions of the embodiments are focused on, and for the part that is not described in detail in a certain embodiment, reference may be made to the related descriptions of other embodiments.
Example 1
As shown in fig. 1 and 2, in some embodiments of the present invention, a method for preparing a composite coating includes the steps of: step one, preparing a first coating 2 on the surface of a substrate 1 by adopting a surface modification process; step two, adopting the surface modification process to manufacture the first coating 2 into a second coating 3; preparing a third coating 4 on the surface of the second coating 3 by adopting the surface modification process to obtain the composite coating; wherein the surface modification process comprises laser cladding, physical vapor deposition, chemical vapor deposition, build-up welding, carburizing treatment and nitriding treatment; the components of the first coating, the second coating and the third coating comprise titanium, chromium, aluminum and carbides and/or nitrides thereof; the substrate comprises iron, copper, titanium, and alloys thereof. In step two, the present invention utilizes at least one of the above-mentioned various surface modification processes to make a new second coating 3 with the made first coating 2 as a "raw material"; that is, the present invention superimposes two of the above surface modification processes to produce an inner layer in the whole composite coating, that is, the above second coating 3, and then produces an outer layer in the whole composite coating on the surface of the above inner layer through the above surface modification process, that is, the whole composite coating includes both the inner layer and the outer layer. The composite coating obtained by the preparation method has better acid corrosion resistance and erosion resistance.
As shown in fig. 2, fig. 2 (a) shows a substrate 1 which has not been subjected to the surface modification process; in some embodiments of the present invention, the substrate 1 in the first step is stainless steel, specifically may be 316 stainless steel, or may be stainless steel of other types according to actual needs.
As shown in fig. 2, fig. 2 (b) shows that the first coating layer 2 is manufactured on the surface of the substrate 1 by the surface modification process, fig. 2 (c) shows that the second coating layer 3 is manufactured by using the first coating layer 2 as a raw material, and fig. 2 (e) shows that the third coating layer 4 is manufactured on the surface of the second coating layer 3 by the surface modification process.
In some embodiments of the present invention, the surface modification processes used in the first and third steps are physical vapor deposition, and the surface modification process used in the second step is laser cladding. Physical vapor deposition (phisical vapor deposition, PVD) means that mass transfer is achieved by physical means, and films with higher strength, good wear resistance, acid etch resistance and other properties can be deposited and prepared on a matrix or substrate with relatively weak comprehensive properties by physical vapor deposition, and the films are composed of particles with extremely small granularity, so that the comprehensive performance of the matrix or substrate can be improved. However, physical vapor deposition has a problem of poor plating around, and when a workpiece having a complicated structure is processed, a detailed position on the complicated workpiece may not be well covered with a coating. The laser cladding can effectively solve the problems of poor surface wear resistance and low hardness of most metal materials; however, when ceramic powder such as TiC and TiN is processed by laser cladding, the ceramic powder has the defect of poor fluidity, so that the ceramic coating prepared by the laser cladding has great difficulty, and the problems of difficult control of the shape of the cladding covered way, uneven surface of a workpiece after processing, high internal porosity of the prepared coating, cracks and the like exist in the laser cladding technology. Firstly, preparing a first coating 2 on the surface of a substrate 1 through a physical vapor deposition process, and then melting and recasting the first coating 2 as a raw material of the laser cladding through the laser cladding to obtain a second coating 3 which is used as an inner layer in the whole composite coating; subsequently, a third coating layer 4 (i.e. the outer layer described above) is formed on the surface of the inner layer (i.e. the second coating layer 3) by a second physical vapor deposition. The particles in the first coating 2 prepared by physical vapor deposition have very small particle size and good wettability and lubricity, so that the first coating 2 can play a role in filling pores in a laser cladding stage, and the problem of high porosity caused by high cooling rate in the laser cladding process is solved.
In some embodiments of the present invention, the components of the first coating layer 2 and the third coating layer 4 are at least one of TiAlCrN, tiN, and CrN, and the components of the second coating layer 3 include TiN and TiC. The invention firstly prepares a first coating layer 2 with at least one of TiAlCrN, tiN and CrN on the surface of a substrate 1 by physical vapor deposition, at the moment, the granularity of at least one of TiAlCrN, tiN and CrN in the first coating layer 2 can reach the micron level, the first coating layer 2 with the granularity is melted again in the following laser cladding and fully fused with TiC and TiN, and the second coating layer 3 is formed after cooling. That is, the second coating 3 is a composite coating obtained by sequentially performing two treatment processes of physical vapor deposition and laser cladding, and the first coating 2 obtained by the first physical vapor deposition is used as a "raw material" for laser cladding, so that the obtained second coating 3 has good acid etching resistance. And, the particle size of the first coating layer 2 prepared by physical vapor deposition and containing at least one of TiAlCrN, tiN and CrN is small, the thermal expansion coefficient is large, and the coating layer has good wettability and lubricity, so that the coating layer can be filled into pores generated by TiN and TiC when being laser cladding in the subsequent laser cladding process. That is, the present invention solves the problem that "ceramic powders such as TiN and TiC are likely to produce voids to weaken the coating strength when laser cladding" by utilizing the point that "TiAlCrN, tiN and CrN produced by physical vapor deposition process have small particle size, large thermal expansion coefficient, and good wettability and lubricity", and the composite coating layer superimposed with physical vapor deposition process and laser cladding process has good acid etching resistance.
However, the mechanical strength of the second coating layer 3 including erosion resistance and the like still fails to meet the more severe requirement standard relatively, so that the present invention further forms the third coating layer 4 with at least one of TiAlCrN, tiN and CrN on the surface of the second coating layer 3 by the second physical vapor deposition means and serves as the outer layer of the whole composite coating layer. The third coating 4 prepared by the physical vapor deposition process and at least one component of TiAlCrN, tiN and CrN has higher hardness and better erosion resistance, so that the whole composite coating has better acid erosion resistance and better mechanical strength including erosion resistance and the like, and the comprehensive performance of the whole composite coating is improved.
In some embodiments of the present invention, the mass ratio of TiN to TiC in the second coating layer 3 is (1-10): 1-10. Specifically, the mass ratio of TiN to TiC may be any of 9:1, 8:2, 7:3, 6:4, 2:1, or 1:1.
In some embodiments of the invention, a laser cladding temperature field simulation model is established through different powder mass ratios of TiN and TiC. Specifically, 316 stainless steel is used as a substrate, the total thickness of the coating is set to be 2mm, and the powder mass ratio of TiN to TiC is respectively TiN/TiC:9/1, 8/2, 7/3, 6/4; simulations have shown that the bath depths obtained according to the above ratios are 2.5mm, 4.1mm, 2.4mm and 2.7mm, respectively, while the bath widths are 18.8mm, 17.6mm, 19.8mm and 20.8mm, respectively. As is known from the general knowledge in the art, the deeper the molten pool, the greater the influence of the cladding area on the substrate, i.e. the greater the range of the heat affected zone of laser cladding, which will affect or even change the structure and performance of the substrate itself, which is not beneficial to the performance and use of the whole workpiece after cladding, so the depth of the molten pool needs to be reduced as much as possible; in addition, on the premise that other condition parameters are consistent, the larger the width of the molten pool is, the better, because the larger the horizontal range of the influence of laser cladding is, the higher the cladding efficiency is. Therefore, according to the above simulation model result data, when the powder mass ratio of TiN and TiC is 7:3, the depth of the molten pool generated by laser cladding is the smallest in the process of preparing the second coating 3, the influence on the substrate 1 is the smallest, and the width of the molten pool is relatively large, so that the better cladding efficiency is ensured, therefore, 7:3 can be used as a preferable powder mass ratio of TiN and TiC.
In some embodiments of the present invention, in the first step, the substrate 1 is subjected to a surface pretreatment before the first coating layer 2 is prepared by using the surface modification process; in the third step, the second coating 3 is subjected to the surface pretreatment before the third coating 4 is prepared by adopting the surface modification process; the surface pretreatment comprises grinding and polishing and cleaning. As shown in fig. 2 (c) and (d), the second coating layer 3 has a rough surface and poor flatness after being formed, and is flattened after the above-mentioned polishing treatment, so that the third coating layer 4 is processed later.
Specifically, in the polishing step, the surface of the sample is sequentially polished by sand paper with the specification of 120# sand paper, 240# sand paper, 400# sand paper, 800# sand paper and 1000# sand paper, then the sample is polished by diamond with the particle size of 0.5-1.2 mu m, and the polished sample is cleaned by alcohol in an ultrasonic cleaning mode and dried for later use. The surface roughness of the substrate 1 is made to be less than Ra0.02 by grinding and polishing so as to reach the standard required by the subsequent physical vapor deposition.
It is worth noting that, before the second physical vapor deposition is adopted to prepare the third coating, a part of pores generated in the process of preparing the second coating by laser cladding can be removed in the process of grinding and polishing, so that the problem of high porosity in the coating prepared by the laser cladding process is further optimized and improved, the porosity of the second coating is further reduced, and the comprehensive properties of the second coating and the whole composite coating including corrosion resistance, erosion resistance and the like are further improved. Therefore, the first coating 2 is prepared by physical vapor deposition, the second coating 3 is prepared by melting the first coating 2 and mixing the first coating 2 with ceramic powder by laser cladding, the porosity in the second coating 3 is low at the moment, and the third coating 4 is prepared on the surface of the second coating 3 by second physical vapor deposition, so that the comprehensive performance of the composite coating is enhanced.
In some embodiments of the invention, the cleaning comprises: and cleaning the substrate by adopting a detergent and clear water in sequence, and then respectively carrying out ultrasonic cleaning on the substrate by adopting propanol and absolute ethyl alcohol. The detergent may be a conventional detergent available on the market specifically for metals.
In some embodiments of the present invention, the process parameters used in the laser cladding are: the laser power is 1300W-2500W, the laser scanning speed is 5-20 mm/s, the powder feeding speed is 10 g/min-40 g/min, and the light spot diameter is 1-5 mm. Illustratively, the laser power may be any of 1300W, 1500W, 1600W, 1700W, 1800W, 2100W, 2350W; the laser scanning speed may be any one of 8mm/s, 10mm/s, 12mm/s, 15mm/s, or 18 mm/s; the powder feeding speed is any one of 15g/min, 20g/min, 25g/min, 30g/min or 35 g/min; the spot diameter is any one of 2mm, 3mm or 4 mm.
In some embodiments of the present invention, the process parameters used in the physical vapor deposition are: the DC power is 1200W-2400W, the DC voltage is 320V-425V, the sputtering voltage is 0.3 Pa-0.8 Pa, the coating time is 3-8 h, and the average film thickness is 2-5 mu m. Illustratively, the dc power is any one of 1350W, 1500W, 1750W, 2000W, or 2200W; the direct current voltage is any one of 335V, 350V, 375V or 400V; the sputtering voltage is any one of 0.4Pa, 0.5Pa, 0.6Pa or 0.7 Pa; the coating time is any one of 4h, 5h, 6h or 7 h; the average film thickness was 3 μm or 4. Mu.m.
In some embodiments of the invention, in step one, the first coating layer 2 having at least one of the components TiAlCrN, tiN, crN is prepared on the surface of the substrate 1 by physical vapor deposition; step two, manufacturing TiN, tiC and the first coating 2 into the second coating 3 by laser cladding; in step three, the third coating layer 4 having at least one of the components TiAlCrN, tiN, crN is produced on the surface of the second coating layer 3 by physical vapor deposition.
It should be noted that, when the TiN, tiC and the first coating layer 2 are manufactured into the second coating layer 3 by using laser cladding in the second step, the first coating layer 2 is melted under the action of laser, and the component (i.e. at least one of TiAlCrN, tiN, crN) in the melted first coating layer 2 is fully fused with the TiN, tiC; in addition, as the first coating 2 is prepared by physical vapor deposition, and TiAlCrN, tiN, crN prepared by physical vapor deposition is micron-sized particles, the coating has good wettability and lubricity, and can be better fused with powder particles of TiN and TiC in the laser cladding process, thereby reducing the porosity in the processed coating caused by the inherent property of the laser cladding process; in other words, the present invention produces the first coating layer 2 having at least one of the components TiAlCrN, tiN, crN by physical vapor deposition, and then uses the first coating layer 2 as a "raw material" for producing the second coating layer 3 by laser cladding, and the "raw material" can exhibit excellent lubricity with TiN and TiC when subjected to laser cladding treatment, thereby reducing the porosity in the coating layer after processing.
In some embodiments of the present invention, the third coating layer 4 may be prepared by chemical vapor deposition, specifically: the method comprises the steps of firstly placing a sample with a second coating 3 in Murakami solution with the mass ratio of KOH: K 3(Fe(CN)6):H2 O= (0.1-2): (9-12) for 25-40 min, then placing the sample in Caro mixed acid solution with the mass ratio of 3:7 of concentrated HCl: H 2O2 for 25-40 min for etching, grinding the sample by diamond micro powder, then ultrasonically cleaning the sample in acetone for at least 5min, and finally preparing a third coating 4 with the component of diamond on the surface of the second coating 3 by a hot wire chemical vapor deposition method so as to further enhance the hardness and the wear resistance of the composite coating.
Example 2
As shown in fig. 2, a composite coating was prepared using the preparation method as described in example 1, and includes: a substrate 1; a second coating layer 3 formed on the substrate 1 and including at least one of TiAlCrN, tiN, crN and TiC; a third coating layer 4 formed on the second coating layer 3, including at least one of TiAlCrN, tiN, crN; wherein the hardness of the third coating layer 4 is larger than that of the second coating layer, so that the third coating layer 4 positioned at the outermost layer plays roles of erosion resistance and abrasion resistance.
It should be noted that, in some embodiments of the present invention, the third coating layer 4 is TiAlCrN obtained by physical vapor deposition, and thus the third coating layer 4 also has good corrosion resistance, but is not as good as the second coating layer 3 obtained by the above-mentioned preparation method, but the hardness of the third coating layer 4 is still higher than the second coating layer 3 obtained by the above-mentioned preparation method, and thus can be regarded as: the third coating 4 is positioned at the outermost side to exert its hardness advantage, and when it is corroded to expose the second coating 3 to the environment, the second coating 3 is rotated to exert the corrosion resistance of the protective substrate 1.
Example 3
Substantially the same as in example 2, the only difference is that:
the sample with the number of 1 to 6 is prepared by taking 316 stainless steel as a substrate, wherein the sample with the number of 1 is the 316 stainless steel which is not subjected to any coating treatment, the sample with the number of 2 is a coating which is prepared by adopting only one-time physical vapor deposition and has the composition of TiAlCrN and the thickness of 3 mu m, the sample with the number of 3 is a coating which is prepared by adopting only laser cladding and has the composition of TiN and TiC and has the thickness of 200 mu m, the sample with the number of 4 is a coating which is prepared by adopting the preparation method provided by the invention, the raw material composition of the first coating and the third coating is CrN, the raw material composition of TiC and TiN and the thickness of 200 mu m when the second coating is prepared by adopting the preparation method provided by the invention, the raw material composition of the first coating and the raw material composition of the third coating is TiN and the raw material composition of the second coating is TiC and the thickness of 200 mu m when the first coating and the third coating is prepared by adopting the preparation method provided by the invention, and the sample with the number of 6 is the raw material composition of TiC and the third coating and the raw material composition of the TiC and the thickness of the third coating is prepared by adopting the preparation method provided by the invention.
The above six samples (each having a 316 stainless steel portion size of 25 x5 mm) were each subjected to different angle washings of 30 °,60 ° and 90 ° according to ASTM G76-2013-related washings, the washings powder used was alumina particles having a particle size of 50 μm, a washout flow rate of 0.033G/s, and a washout time of 5min, and table 1 below was obtained.
Table 1 erosion loss for samples No. 1 to 6
As shown in table 1, the samples No. 4 to No. 6 prepared by the preparation method provided by the invention have less erosion loss in the erosion experiment, and show better erosion resistance; therefore, the preparation method provided by the invention can be applied to rotor protection of the water-spraying oil-free screw compressor, and the coating obtained by the preparation method can enhance erosion resistance of the rotor.
As shown in table 1, the acid etch amount of sample No. 6 was less than that of samples No. 4 and No. 5, indicating that: on the premise of preparing TiC and TiN into the second coating by laser cladding, when TiAlCrN is adopted as the components of the first coating and the third coating, the whole composite coating can obtain better erosion resistance. Because the TiAlCrN increases Al element relative to TiN and CrN, after Al atoms replace a part of Ti atoms in the TiN coating and a part of Cr atoms in the CrN coating, the crystal lattice in the coating is sufficiently distorted, the crystal boundary is increased and dislocation is more and is not easy to slip due to sufficient crystal lattice distortion, so that the wear resistance and hardness of the obtained coating material are improved, and the erosion resistance of the whole coating is also improved; the multi-element composite coating formed by multiple elements of Ti, al and Cr combines the excellent performances of all metal elements, and the coating performance is greatly improved. Thus, as a preferred embodiment of the present invention, the components of the first coating layer and the third coating layer each comprise TiAlCrN, and the components of the second coating layer comprise TiC and TiN, so that the entire composite coating layer obtains better erosion resistance.
Example 4
Substantially the same as in example 2, the only difference is that:
The sample with the number of 7 to 12 is prepared by taking 316 stainless steel as a substrate, wherein the sample with the number of 7 is the 316 stainless steel which is not subjected to any coating treatment, the sample with the number of 8 is a coating with the composition of TiAlCrN and the thickness of 3 mu m, which is prepared by adopting only one-time physical vapor deposition, the sample with the number of 9 is a coating with the composition of TiN and TiC and the thickness of 200 mu m, which is prepared by adopting only laser cladding, the sample with the number of 10 is a coating with the composition of TiC and the thickness of 200 mu m, which is prepared by adopting the preparation method provided by the invention, when the first coating and the third coating are both CrN and the composition of TiC and TiN and the thickness of 200 mu m are both prepared by adopting the preparation method provided by the invention, and the sample with the composition of TiC and the thickness of 200 mu m are both prepared by adopting the preparation method provided by the invention, and the sample with the composition of 11 is prepared by adopting the preparation method provided by the invention, and the raw material composition of TiC and the third coating is prepared by adopting the composition of 200 mu m and the thickness of TiC and the coating is prepared by adopting the preparation method provided by the preparation method.
According to the acid etch test standard of GB/T40338-2021, the acid etch test was performed for a total period of 30d on the above samples No. 7 to 12 using concentrated hydrochloric acid at a concentration of 13.5g/L at room temperature (28 ℃ C.), wherein the above samples were weighed during the acid etch tests of 3d, 7d and 30d to obtain mass loss conditions of the above samples, thereby obtaining Table 2 below.
TABLE 2 erosion loss for samples No. 7 to 12
As shown in table 2, the samples numbered 10 to 12 prepared by the preparation method provided by the invention have less acid etching loss in the acid etching experiment and show better acid etching resistance; therefore, the preparation method provided by the invention can be applied to rotor protection of the water-spraying oil-free screw compressor, and the coating obtained by the preparation method can enhance the acid corrosion resistance of the rotor.
As shown in table 2, the acid etching amount of sample No. 12 was smaller than that of samples No. 10 and No. 11, which indicates that: on the premise of preparing TiC and TiN into the second coating by laser cladding, when TiAlCrN is adopted as the components of the first coating and the third coating, the whole composite coating can obtain better acid corrosion resistance. Because the TiAlCrN increases Al element relative to TiN and CrN, after Al atoms replace a part of Ti atoms in the TiN coating and a part of Cr atoms in the CrN coating, the crystal lattice in the coating is sufficiently distorted, the crystal boundary is increased and dislocation is more and is not easy to slip due to sufficient crystal lattice distortion, and the acid etching resistance of the obtained coating material is improved; the multi-element composite coating formed by multiple elements of Ti, al and Cr combines the excellent performances of all metal elements, and the coating performance is greatly improved. Thus, as a preferred embodiment of the present invention, the components of the first coating and the third coating each comprise TiAlCrN, and the components of the second coating comprise TiC and TiN, so that the overall composite coating achieves better acid etch resistance.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. Furthermore, the foregoing description of the principles and embodiments of the invention has been provided for the purpose of illustrating the principles and embodiments of the invention and for the purpose of providing a further understanding of the principles and embodiments of the invention, and is not to be construed as limiting the invention.

Claims (9)

1. A method for preparing a composite coating, the method comprising the steps of:
step one, preparing a first coating with at least one of components TiAlCrN, tiN, crN on the surface of a substrate through physical vapor deposition;
Step two, preparing TiN, tiC and the first coating into a second coating through laser cladding;
Preparing a third coating with at least one of components TiAlCrN, tiN, crN on the surface of the second coating by physical vapor deposition;
the substrate comprises iron, copper, titanium, and alloys thereof.
2. The method according to claim 1, wherein the substrate in the first step is stainless steel.
3. The method of claim 1, wherein the first and third coating layers comprise at least one of TiAlCrN, tiN, and CrN, and the second coating layer comprises a mixture of TiN and TiC and the first coating layer.
4. The method of claim 3, wherein the mass ratio of TiN to TiC in the mixture of TiN and TiC in the second coating layer is (1-10): 1-10.
5. The method according to claim 1, wherein in the first step, the substrate is subjected to surface pretreatment before the first coating is formed by a physical vapor deposition process;
in the third step, the surface pretreatment is carried out on the second coating before the third coating is prepared by adopting a physical vapor deposition process;
The surface pretreatment comprises grinding and polishing and cleaning.
6. The method of preparing according to claim 5, wherein the washing comprises:
And cleaning the substrate by adopting a detergent and clear water in sequence, and then respectively carrying out ultrasonic cleaning on the substrate by adopting propanol and absolute ethyl alcohol.
7. The method according to any one of claims 1 to 6, wherein the process parameters used in the laser cladding are: the laser power is 1300W-2500W, the laser scanning speed is 5-20 mm/s, the powder feeding speed is 10 g/min-40 g/min, and the light spot diameter is 1-5 mm.
8. The method according to any one of claims 1 to 6, wherein the process parameters used in the physical vapor deposition are: the DC power is 1200W-2400W, the DC voltage is 320V-425V, the sputtering voltage is 0.3 Pa-0.8 Pa, the coating time is 3-8 h, and the average film thickness is 2-5 mu m.
9. A composite coating produced by the production method according to any one of claims 1 to 8, and comprising:
a substrate;
A second coating layer formed on the substrate, comprising a mixture of at least one of TiAlCrN, tiN, crN with TiN and TiC;
A third coating layer formed over the second coating layer, including at least one of TiAlCrN, tiN, crN;
wherein the hardness of the third coating is greater than the hardness of the second coating.
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