CN114921738B - Method for forming surface coating, composite material and application thereof - Google Patents
Method for forming surface coating, composite material and application thereof Download PDFInfo
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- CN114921738B CN114921738B CN202210444820.4A CN202210444820A CN114921738B CN 114921738 B CN114921738 B CN 114921738B CN 202210444820 A CN202210444820 A CN 202210444820A CN 114921738 B CN114921738 B CN 114921738B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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Abstract
The invention discloses a forming method of a surface coating, a composite material and application thereof, wherein the forming method of the surface coating comprises the following steps of S110: mixing a strengthening substance and an adhesive according to a mass ratio of 5:1-15 to prepare a coating material, wherein the strengthening substance is selected from at least one of zirconium, aluminum, chromium and titanium, and the adhesive is selected from at least one of nitrovarnish, polyacrylate and vinyl acetate; step S120: coating the coating material on the surface of a substrate to form a coating layer on the surface of the substrate, wherein the surface of the substrate is columnar crystal; step S130: and carrying out a laser quenching process on the substrate with the coating layer in an inert gas atmosphere. The method for forming the surface coating realizes the effective composition of the substrate and the coating on the premise of not influencing the property and the shape of the substrate, and the hardness and the high-temperature oxidation resistance of the original substrate material can be effectively improved by the method for forming the coating.
Description
Technical Field
The invention relates to the field of metallurgical materials, in particular to a forming method of a surface coating, a composite material and application thereof.
Background
In order to meet the requirements of high efficiency and high thrust-weight ratio of engines in the fields of aviation and navigation, the inlet temperature of a turbine reaches to even far higher than the maximum working temperature of a high-temperature blade, and the mechanical property and chemical stability of the high-temperature blade cannot be ensured only by the material of the high-temperature blade under the extreme operating environment, so that in order to improve the mechanical property and chemical stability of parts such as the blade, the traditional method is to form a coating on the surface of the high-temperature blade by a chemical vapor deposition method.
However, the deposition temperature of chemical vapor deposition is between 900 ℃ and 2000 ℃ in the process of forming the coating, and the deformation or the change of the structure of the part is easily caused by the excessively high temperature, further, the mechanical property of the part material is reduced, the bonding force between the part material and the coating is weakened, and the mechanical property and the chemical stability of the finally formed part material containing the coating still cannot meet the actual requirement.
Disclosure of Invention
Based on this, in order to simultaneously improve the hardness and the high temperature oxidation resistance of the material, it is necessary to provide a surface coating forming method, a composite material and applications thereof.
The invention provides a method for forming a surface coating, which comprises the following steps:
s110: mixing a strengthening substance and an adhesive according to a mass ratio of 5:1-15 to prepare a coating material, wherein the strengthening substance is selected from at least one of zirconium, aluminum, chromium and titanium, and the adhesive is selected from at least one of nitrovarnish, polyacrylate and vinyl acetate;
s120: coating the coating material on the surface of a substrate to form a coating layer on the surface of the substrate, wherein the surface of the substrate is columnar crystal;
s130: carrying out laser quenching process treatment on the substrate with the coating layer in a protective gas atmosphere, wherein the parameters of the laser quenching process comprise: the laser output power is 260W-350W, the laser beam scanning speed is 600 mm/s-1100 mm/s, the irradiation frequency is 5-15 times, and the laser energy density is 50J/cm 2 ～120J/cm 2 。
In one embodiment, the particle size of the reinforcing material is 5 μm to 87 μm.
In one embodiment, after step S120 and before step S130, a step of drying the substrate having the coating layer is further included.
In one embodiment, the parameters of the laser quenching process further include: the diameter of the laser spot is 0.05 mm-0.2 mm, and the laser repetition frequency is 0.05 Hz-0.3 Hz.
In one embodiment, the protective gas is selected from at least one of argon and nitrogen.
In one embodiment, the thickness of the coating layer is 0.05mm to 0.2mm.
Further, the invention also provides a composite material, which comprises a substrate and a coating formed on the surface of the substrate according to the surface coating forming method.
In one embodiment, the substrate is a nickel-base superalloy.
In one embodiment, the nickel-base superalloy comprises, in weight percent: 0.05 to 0.5 percent of aluminum, 10 to 22 percent of chromium, 10 to 25 percent of iron, 0.01 to 0.15 percent of manganese, 1 to 6 percent of molybdenum, 1 to 8 percent of niobium, 0.1 to 1 percent of silicon, 0.1 to 2 percent of titanium, 0.01 to 0.05 percent of tungsten, 0.01 to 0.08 percent of carbon, 0.01 to 0.08 percent of oxygen and 45 to 66 percent of nickel.
Still further, the present invention also provides for the use of the above-described composite material in the preparation of a hot end component.
The matrix with the columnar crystal structure surface and the coating are effectively compounded on the premise of not influencing the property and the shape of the matrix by coating the strengthening substance and the adhesive on the surface of the matrix and then carrying out laser quenching treatment and matching with the limitation of specific laser parameters, the irradiation times and the laser scanning speed, so that the problems of reducing the mechanical property of the matrix material and weakening the binding force between the matrix material and the coating caused by high deposition temperature in the traditional chemical vapor deposition can be effectively avoided. The method for forming the coating can effectively improve the hardness and the high-temperature oxidation resistance of the original base material, and the base material with the coating and the surface columnar crystals can be widely applied to severe working conditions such as high temperature, high strength and the like.
Drawings
FIG. 1 is a scanning electron microscope image of zirconium powder as a reinforcing material;
FIG. 2 is a good bond between the Inconel718 alloy and the zirconium coating in example 1 (substrate on the left and coating on the right);
fig. 3 shows that the Inconel718 alloy and the zirconium coating in comparative example 2 are obviously peeled off when the coating is insulated for 50h at the high temperature of 1000 ℃ (the left is the matrix, and the right is the coating).
Detailed Description
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a method for forming a surface coating, which comprises the following steps of S110 to S130.
Step S110: mixing a strengthening substance and an adhesive according to a mass ratio of 5:1-15 to prepare the coating material, wherein the strengthening substance is selected from at least one of zirconium, aluminum, chromium and titanium, and the adhesive is selected from at least one of nitrovarnish, polyacrylate and vinyl acetate.
It can be understood that the mass ratio of the reinforcing substance to the adhesive is 8:1-12, and specifically the mass ratio of the reinforcing substance to the adhesive can be, but is not limited to 8:1, 9:1, 10.
In one particular example, the reinforcing substance has a particle size of 5 μm to 87 μm.
Further, the particle size of the reinforcing material D50 is 36 μm to 70 μm, and specifically, the particle size of the reinforcing material may be, but not limited to, 36 μm, 40 μm, 44 μm, 48 μm, 52 μm, 56 μm, 58 μm, 60 μm, 62 μm, 64 μm, 68 μm or 70 μm. It will be appreciated that a reinforcing substance having a particle size within the above-described ranges may be effectively mixed with the binder and applied to the substrate.
Preferably, the strengthening substance is zirconium, and as shown in fig. 1, is a scanning electron micrograph of zirconium powder.
Step S120: and coating the coating material on the surface of the substrate to form a coating layer on the surface of the substrate, wherein the surface of the substrate is columnar crystal.
In a specific example, the thickness of the coating layer is 0.05mm to 0.2mm.
Further, the thickness of the coating layer is 0.1mm to 0.15mm, and specifically, the thickness of the coating layer that can achieve effective coating may be, but is not limited to, 0.1mm, 0.11mm, 0.12mm, 0.13mm, 0.14mm, or 0.15mm.
In a specific example, after step S120 and before step S130, a step of drying the substrate having the coating layer is further included.
Furthermore, the drying temperature is 180-240 ℃, and the drying time is 3-7 hours. Preferably, the drying temperature is 1850-220 ℃, and the drying time is 4-6 hours.
Step S130: and carrying out a laser quenching process on the substrate with the coating layer in an inert gas atmosphere.
Wherein, the parameters of the laser quenching process comprise: the laser output power is 260W-350W, the laser beam scanning speed is 600 mm/s-1100 mm/s, the irradiation frequency is 5-15 times, and the laser energy density is 50J/cm 2 ～120J/cm 2 。
Further, the laser output power is 280W to 320W, and specifically, the laser output power may be, but not limited to, 280W, 285W, 290W, 295W, 300W, 305W, 310W, 315W, or 320W.
Further, the laser beam scanning speed is 800mm/s to 1100mm/s, and specifically, the laser beam scanning speed may be, but not limited to, 800mm/s, 900mm/s, 1000mm/s, or 1100mm/s.
Specifically, the number of irradiation times may be, but is not limited to, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, and then 15 times.
Preferably, the laser energy density is 80J/cm 2 ～120J/cm 2 In particular, the laser fluence may be, but is not limited to, 80J/cm 2 、85J/cm 2 、90J/cm 2 、95J/cm 2 、100J/cm 2 、105J/cm 2 、110J/cm 2 、115J/cm 2 Or 120J/cm 2 。
In a specific example, the inert gas is selected from at least one of argon and nitrogen. Preferably, the inert gas is argon.
In one specific example, laser quenchingThe parameters of the fire process also include: vacuum degree of 10 -3 Pa～10 -2 Pa, the diameter of the laser spot is 0.05 mm-0.2 mm, and the laser repetition frequency is 0.05 Hz-0.3 Hz.
It is understood that the degree of vacuum refers to the degree of vacuum within the response apparatus in performing the laser quenching process.
Further, the degree of vacuum in the laser quenching process may be, but is not limited to, 10 -3 Pa、2×10 -3 Pa、4×10 - 3 Pa、6×10 -3 Pa、8×10 -3 Pa、9×10 -3 Pa or 10 -2 Pa. The good vacuum degree can effectively avoid the influence of foreign impurities or further reaction with gas in the air on the formation of the compact coating in the laser quenching process.
Still further, the diameter of the laser spot may be, but is not limited to, 0.05mm, 0.1mm, 0.15mm, or 0.2mm.
Preferably, the laser repetition rate is 0.05Hz to 0.2Hz, and particularly, the laser repetition rate may be, but not limited to, 0.05Hz, 0.1Hz, 0.15Hz, 0.2Hz, 0.25Hz, or 0.3Hz.
The matrix with the columnar crystal structure surface and the coating are effectively compounded on the premise of not influencing the property and the shape of the matrix by coating the strengthening substance and the adhesive on the surface of the matrix and then carrying out laser quenching treatment in cooperation with the limitation of specific laser parameters, irradiation times and laser scanning speed, so that the problems of reducing the mechanical property of the matrix material and weakening the binding force between the matrix material and the coating caused by high deposition temperature in the traditional chemical vapor deposition can be effectively avoided. The method for forming the coating can effectively improve the hardness and the high-temperature oxidation resistance of the original base material, and the base material with the coating and the surface columnar crystal structure can be widely applied to severe working conditions such as high temperature, high strength and the like.
Further, the present invention also provides a composite material comprising a substrate and a coating layer formed on the surface of the substrate according to the method for forming a surface coating layer as described above. Preferably, the substrate is a nickel-based superalloy.
In one specific example, the nickel-base superalloy comprises the following raw material composition in percentage by weight: 0.05 to 0.5 percent of aluminum, 10 to 22 percent of chromium, 10 to 25 percent of iron, 0.01 to 0.15 percent of manganese, 1 to 6 percent of molybdenum, 1 to 8 percent of niobium, 0.1 to 1 percent of silicon, 0.1 to 2 percent of titanium, 0.01 to 0.05 percent of tungsten, 0.01 to 0.08 percent of carbon, 0.01 to 0.08 percent of oxygen and 45 to 66 percent of nickel.
Preferably, the nickel-based superalloy comprises, by weight, 0.1% -0.5% of aluminum, 12% -20% of chromium, 13% -22% of iron, 0.03% -0.1% of manganese, 1.5% -5% of molybdenum, 2% -6% of niobium, 0.1% -0.8% of silicon, 0.3% -1.5% of titanium, 0.01% -0.03% of tungsten, 0.02% -0.06% of carbon, 0.02% -0.06% of oxygen, and 49% -64% of nickel.
Preferably, the nickel-based superalloy is an Inconel718 nickel-based superalloy, which has a main columnar crystal in a vertical plane and a small amount of equiaxed crystals inside.
In one particular example, the average grain size of the nickel-base superalloy is between 90 μm and 120 μm.
It is understood that the crystalline form of the nickel-base superalloy may be, but is not limited to, columnar.
Further, the average grain size of the nickel-base superalloy may be, but is not limited to, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, or 120 μm.
It is understood that the above average grain size is the average diameter of grains counted by the EDSD experiment.
Further, the present invention also provides for the use of the above-described composite material in the preparation of a hot end component.
The method has the advantages that the strengthening substance and the adhesive are coated on the surface of the nickel-based superalloy and then subjected to laser quenching treatment, so that the nickel-based superalloy and the coating are effectively compounded on the premise of not influencing the property and the shape of the nickel-based superalloy, and the problems that the mechanical property of the nickel-based superalloy is reduced and the bonding force between the nickel-based superalloy and the coating is weakened due to high deposition temperature in the traditional chemical vapor deposition can be effectively solved. The method for forming the coating can effectively improve the hardness and the high-temperature oxidation resistance of the original nickel-based superalloy, the nickel-based superalloy with the coating can be widely applied to severe working conditions such as high temperature, high strength and the like, for example, the composite material of the nickel-based superalloy, of which the surface forms a corresponding coating structure, can be used for preparing a hot end part used for a nuclear reactor, an aeroengine, an aerospace vehicle or a gas turbine without limitation.
Specific examples are provided below to further illustrate the nickel-base superalloy and the surface coating composite material of the present invention. The raw materials in the following embodiments are commercially available unless otherwise specified.
The nickel-base superalloy has the brand number Inconel718, and the composition table of the alloy is as follows.
TABLE 1 Inconel718 alloy composition Table
Example 1
The embodiment provides a method for forming a coating on the surface of a nickel-based superalloy by using the nickel-based superalloy as a substrate, which comprises the following specific steps:
step S110: a pneumatic powder sieving device is used for selecting a 240-mesh screen to control the particle size of the powder, and finally, undersize powder is selected, namely the particle size of the powder is about 60 mu m. Then, the zirconium powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by a layer by using a fine brush, and repeating the process repeatedly until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, putting the nickel-based high-temperature alloy with the coating layer into a vacuum drying oven, firstly vacuumizing the drying oven until the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature, and taking out.
Step S130: the nickel-based superalloy with the coating layer is subjected to a laser quenching process in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1000mm/s, the spot size is 0.1mm, the irradiation is carried out for 10 times, the repetition frequency is 0.1Hz, and the energy density is 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
As shown in FIG. 2, which is a scanning electron microscope image of the composite of the substrate and the coating layer of the present embodiment, the Vickers hardness of the surface of the nickel-based superalloy provided by the present embodiment reaches 720 + -20 HV, and the composite nickel-based superalloy is not subjected to surface oxidation aging after being subjected to heat preservation at 1000 ℃ for 100 hours.
Example 2
The embodiment provides a method for forming a coating on the surface of a nickel-based superalloy by using the nickel-based superalloy as a substrate, which comprises the following specific steps:
step S110: and (3) selecting a 240-mesh screen by using a pneumatic powder screening device to control the particle size of the powder, and finally selecting undersize powder, namely the particle size of the powder is about 60 mu m. Then, the zirconium powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, putting the nickel-based high-temperature alloy with the coating layer into a vacuum drying oven, firstly vacuumizing the drying oven until the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature and taking out.
Step S130: the nickel-based superalloy with the coating layer is subjected to a laser quenching process in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1000mm/s, the spot size is 0.1mm, the irradiation is carried out for 5 times, the repetition frequency is 0.1Hz, and the energy density is 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
The surface Vickers hardness of the compounded nickel-based superalloy provided by the embodiment reaches 680 +/-11 HV, and the compounded nickel-based superalloy is kept at the high temperature of 1000 ℃ for 100 hours without surface oxidation aging.
Example 3
The present embodiment provides a titanium alloy TC18, which has the following composition table as shown in table 2 below, and forms a coating on the surface thereof, and the specific steps are as follows:
step S110: a pneumatic powder sieving device is used for selecting a 240-mesh screen to control the particle size of the powder, and finally, undersize powder is selected, namely the particle size of the powder is about 60 mu m. Then, the zirconium powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, the titanium alloy with the coating layer is placed into a vacuum drying oven, the drying oven is firstly vacuumized, and the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature, and taking out.
Step S130: carrying out a laser quenching process on the titanium alloy with the coating layer in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1000mm/s, the spot size is 0.1mm, the irradiation is carried out for 5 times, the repetition frequency is 0.1Hz, and the energy density is 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
The Vickers hardness of the surface of the compounded titanium alloy TC18 reaches 340 +/-20 HV, and the surface oxidation aging does not occur after the heat preservation is carried out for 100 hours at the high temperature of 600 ℃.
TABLE 2 ingredient Table of TC18
Example 3
The embodiment provides a titanium alloy TC18 as a substrate, and a coating is formed on the surface of the substrate, and the method comprises the following specific steps:
step S110: a pneumatic powder sieving device is used for selecting a 240-mesh screen to control the particle size of the powder, and finally, undersize powder is selected, namely the particle size of the powder is about 60 mu m. Then, the aluminum powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, the titanium alloy with the coating layer is placed into a vacuum drying oven, the drying oven is firstly vacuumized, and the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature and taking out.
Step S130: carrying out a laser quenching process on the titanium alloy with the coating layer in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1000mm/s, the spot size is 0.1mm, the irradiation is carried out for 5 times, the repetition frequency is 0.1Hz, and the energy density is 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
The Vickers hardness of the surface of the compounded titanium alloy TC18 reaches 380 +/-20 HV, and the surface oxidation aging does not occur after the heat preservation is carried out for 100 hours at the high temperature of 600 ℃.
Comparative example 1
The comparative example provides a method for forming a coating on the surface of a nickel-based superalloy by using the nickel-based superalloy as a substrate, which comprises the following steps:
step S110: a pneumatic powder sieving device is used for selecting a 240-mesh screen to control the particle size of the powder, and finally, undersize powder is selected, namely the particle size of the powder is about 60 mu m. Then, the zirconium powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, putting the nickel-based high-temperature alloy with the coating layer into a vacuum drying oven, firstly vacuumizing the drying oven until the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature, and taking out.
Step S130: the nickel-based superalloy with the coating layer is subjected to a laser quenching process in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1000mm/s, the spot size is 0.1mm, the irradiation is carried out for 20 times, the repetition frequency is 0.1Hz, and the energy density is 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
The surface Vickers hardness of the compounded nickel-based high-temperature alloy reaches 709 +/-9.8 HV, and the nickel-based high-temperature alloy is subjected to heat preservation for 100 hours at the high temperature of 1000 ℃ to generate severe oxidation aging.
Comparative example 2
The comparative example provides a method for forming a coating on the surface of a nickel-based superalloy by using the nickel-based superalloy as a substrate, which comprises the following steps:
step S110: a pneumatic powder sieving device is used for selecting a 240-mesh screen to control the particle size of the powder, and finally, undersize powder is selected, namely the particle size of the powder is about 60 mu m. Then, the zirconium powder and the adhesive are mixed according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of 1 mm. After the coating layer is manufactured, putting the nickel-based high-temperature alloy with the coating layer into a vacuum drying oven, firstly vacuumizing the drying oven until the vacuum degree reaches 10 -1 After Pa, at 2Drying at 00 ℃ for 5 hours, cooling to room temperature and taking out.
Step S130: the nickel-based superalloy with the coating layer is subjected to a laser quenching process in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: the laser output power is 300W, the scanning speed is 1200mm/s, the spot size is 0.1mm, the irradiation is carried out for 5 times, the repetition frequency is 0.1Hz, and the energy density is 50J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
As shown in fig. 3, the surface of the coating of the nickel-based superalloy obtained by the present comparative example has a small amount of pores under a scanning electron microscope, and the coating and the nickel-based superalloy do not achieve complete metallurgical bonding. The Vickers hardness of the obtained surface reaches 615 +/-13 HV, and the coating is obviously peeled off after heat preservation for 50 hours at the high temperature of 1000 ℃.
Comparative example 3
The comparative example provides a method for forming a coating on the surface of a nickel-based superalloy by using the nickel-based superalloy as a substrate, which comprises the following steps:
step S110: and (3) selecting a 240-mesh screen by using a pneumatic powder screening device to control the particle size of the powder, and finally selecting undersize powder, namely the particle size of the powder is about 60 mu m. And then putting the sieved iron powder into a beaker container according to the mass ratio of 10. Stirring the mixture at a constant speed by using a glass rod until the mixture is fully mixed to prepare a coating material;
step S120: and lightly brushing the coating material on the surface of the alloy by using a fine brush, and repeatedly brushing the coating material back and forth for multiple times until the surface of the alloy coated with the coating material is flat to form a coating layer with the thickness of about 1 mm. After the coating layer is manufactured, the titanium alloy with the coating layer is placed into a vacuum drying oven, the drying oven is firstly vacuumized, and the vacuum degree reaches 10 -1 And after Pa, drying at 200 ℃ for 5 hours, cooling to room temperature, and taking out.
Step S130: the nickel-based superalloy with the coating layer is subjected to a laser quenching process in an inert gas argon atmosphere, wherein the parameters selected by the laser quenching process are as follows: laser output power 300W, scanning speed 1000mm/s, spot size 0.1mm, irradiation 5 times, repetition frequency0.1Hz, energy density 100J/cm 2 . In the laser beam treatment process, the vacuum degree of the chamber is ensured to reach 9 multiplied by 10 -3 Pa。
The surface Vickers hardness of the compounded nickel-based high-temperature alloy reaches 220 +/-15 HV, and the nickel-based high-temperature alloy is subjected to heat preservation for 50 hours at the high temperature of 300 ℃ to generate severe oxidation aging.
Through the comparison between the comparative example 1 and the example 1, it can be seen that although the increase of the number of irradiation times has little influence on the hardness of the surface of the composite material of the nickel-based superalloy and the surface coating, the oxidation resistance of the surface of the composite material is greatly reduced, and through the comparison between the comparative example 2 and the example 1, it can be seen that the surface of the composite material cannot obtain the hardness and the oxidation resistance at the same time by increasing the scanning speed of the laser beam and reducing the energy density, so that the composite material has a good effect. After laser quenching, the strengthening substance permeates into the substrate with the surface in a columnar crystal structure to generate a fine alloy material, so that the metallurgical bonding with the substrate can be strengthened, the surface crystal grains are refined, and the laser surface phase change and laser surface crystal grain refining effects are achieved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention and obtained by logical analysis, reasoning or limited experiments by those skilled in the art are all within the scope of the appended claims. Therefore, the protection scope of the patent of the invention is subject to the content of the appended claims, and the description can be used for explaining the content of the claims.
Claims (10)
1. A method of forming a surface coating, comprising the steps of:
s110: mixing a strengthening substance and an adhesive according to a mass ratio of 5:1-15 to prepare a coating material, wherein the strengthening substance is selected from at least one of zirconium, aluminum, chromium and titanium, and the adhesive is selected from at least one of nitrovarnish, polyacrylate and vinyl acetate;
s120: coating the coating material on the surface of a substrate to form a coating layer on the surface of the substrate, wherein the surface of the substrate is columnar crystal;
s130: carrying out laser quenching process treatment on the substrate with the coating layer in a protective gas atmosphere, wherein the parameters of the laser quenching process comprise: the laser output power is 260W-350W, the laser beam scanning speed is 600 mm/s-1100 mm/s, the irradiation times are 5-15 times, and the laser energy density is 50J/cm 2 ～120J/cm 2 ，
Wherein the substrate is nickel-based superalloy or titanium alloy TC18.
2. The method of forming a surface coating according to claim 1, wherein the reinforcing material has a particle size of 5 μm to 87 μm.
3. The method for forming a surface coating according to claim 1, further comprising a step of drying the substrate having the coating layer after step S120 and before step S130.
4. The method of forming a surface coating of claim 1, wherein the parameters of the laser quenching process further comprise: the diameter of the laser spot is 0.05 mm-0.2 mm, and the laser repetition frequency is 0.05 Hz-0.3 Hz.
5. The method of forming a surface coating according to claim 1, wherein the protective gas is at least one selected from the group consisting of argon and nitrogen.
6. The method of forming a surface coating according to any one of claims 1 to 5, wherein the coating layer has a thickness of 0.05mm to 0.2mm.
7. A composite material comprising a substrate and a coating layer formed on the surface of the substrate by the method for forming a surface coating layer according to any one of claims 1 to 6.
8. The composite material of claim 7, wherein the substrate is a nickel-based superalloy.
9. The composite material of claim 8, wherein the nickel-base superalloy has an elemental composition comprising, in weight percent: 0.05 to 0.5 percent of aluminum, 10 to 22 percent of chromium, 10 to 25 percent of iron, 0.01 to 0.15 percent of manganese, 1 to 6 percent of molybdenum, 1 to 8 percent of niobium, 0.1 to 1 percent of silicon, 0.1 to 2 percent of titanium, 0.01 to 0.05 percent of tungsten, 0.01 to 0.08 percent of carbon, 0.01 to 0.08 percent of oxygen and 45 to 66 percent of nickel.
10. Use of a composite material according to any one of claims 7 to 9 in the preparation of a hot end component.
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