CN113651619A - High-entropy ceramic powder for marine diesel engine, application and application method - Google Patents
High-entropy ceramic powder for marine diesel engine, application and application method Download PDFInfo
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Abstract
The invention relates to high-entropy ceramic powder for marine diesel engines, application and an application method thereof, wherein the ceramic powder is high-entropy boride (HfZrMoNbTi) B formed by six elements of Hf, Zr, Mo, Nb, Ti and B2Wherein the mole percentage of Hf, Zr, Mo, Nb and Ti is 5-35%, the mole ratio of metal element to B element in the ceramic powder body is 1:2.1-1:2.5, and the excessive B can counteract the loss brought by metal reaction and sintering. The obtained powder was plasma sprayedOn the surface of the exhaust valve rod of the diesel engine, the capability of the valve rod for resisting high-temperature deformation, corrosion erosion and abrasion is improved, the replacement cost is saved, and the potential safety hazard is reduced.
Description
Technical Field
The invention relates to high-entropy ceramic powder and a specific application and an application method thereof, in particular to high-entropy ceramic powder for an exhaust valve rod of a marine diesel engine, and an application method thereof.
Background
The marine diesel engine is the core of a ship power system and is also a part with severe working conditions in the running process of a ship, the exhaust valve rod is a vulnerable part in the diesel engine, and the deformation and the fracture of the exhaust valve often cause serious faults of the diesel engine to cause serious economic loss. When the exhaust valve rod reciprocates, the alternating load born by the exhaust valve rod can reach 30 kN at most, and the exhaust valve rod can bear the rapid scouring of corrosive gas at the temperature of 2000 ℃. Under the combined action of corrosion, alternating stress, thermal stress and abrasion, the fatigue crack on the surface of the exhaust valve rod is rapidly initiated and expanded to cause the fracture failure of the exhaust valve rod. During the operation of the diesel engine, the broken valve rod can cause the valve disc to fall off and enter the combustion chamber to collide with the piston to induce the breakage of the connecting rod, so that the engine body breaks down. In order to reduce the potential safety hazard and economic loss, the mechanical performance of the exhaust valve rod needs to be improved, so that the service life of the valve rod is prolonged. Because valve stem damage tends to occur first on the valve stem surface, thermal spray techniques to produce high performance coatings on valve stem surfaces are an efficient and low cost method of poppet valve stem performance.
In the existing method, the surface of the valve rod is protected by using thermal spraying technologies such as plasma spraying, electric arc spraying and the like, and high-temperature-resistant alloy materials and metal ceramic materials are often selected as spraying materials. In combination with the working environment of the valve rod, the surface of the valve rod needs to have excellent high temperature resistance, impact resistance, fatigue resistance and corrosion resistance. The mechanical property of the alloy coating is poor in high-temperature environment, the alloy coating cannot effectively resist the erosion of corrosive gas, although the mechanical property of the metal ceramic coating is superior to that of the alloy coating, the corrosion resistance of the metal ceramic coating is poor, and part of carbide ceramic can also generate decarburization phenomenon in the high-temperature environment. Therefore, it becomes very important to develop a coating which is suitable for the environment and has better corrosion resistance.
Disclosure of Invention
The invention aims to provide high-entropy ceramic powder for a marine diesel engine, which is used on the surface of an exhaust valve rod of the diesel engine, so that the capability of the valve rod in resisting high-temperature deformation, corrosion scouring and abrasion is improved, the replacement cost is saved, and the potential safety hazard is reduced.
The technical purpose of the invention is realized by the following technical scheme:
the high-entropy ceramic powder for the marine diesel engine is high-entropy boride (HfZrMoNbTi) B formed by six elements including Hf, Zr, Mo, Nb, Ti and B2Wherein the mole percentage of Hf, Zr, Mo, Nb and Ti is 5-35%.
Preferably, the molar ratio of the metal element to the B element in the ceramic powder is 1:2.1-1:2.5, and the excessive B can counteract the loss caused by the reaction with the metal and sintering.
Preferably, the ceramic powder is prepared by the following operation steps,
A1. weighing metal powder and boron powder according to the mol percentage, putting the metal powder and the boron powder into a vacuum high-energy ball mill, and ball-milling and mixing;
A2. and (3) carrying out vacuum plasma sintering on the powder obtained in the step A1, grinding the powder, and screening to obtain the target product.
Preferably, the powder particle size of the metal powder and the boron powder in step A1 is 1-5 μm.
Preferably, the ball milling in step A1 is carried out for 2-8 h, and the mixture is cooled for 30 min after each 1 h of mixing.
Preferably, the specific preparation process comprises the following steps:
A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mol percentage, wherein the purity of each element powder is more than 99 percent, the particle size of the powder is 1-5 mu m, the powder is placed into a vacuum high-energy ball mill, the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 3:1-4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, the cooling is carried out for 30-60 min after the ball milling and mixing are carried out for 1-2 h, and the mixing time is 2-8 h;
A2. and (3) carrying out vacuum plasma sintering on the obtained mixed powder for 5-10 min, grinding the powder and screening to obtain the spraying powder.
The second purpose of the invention is to provide a specific application of the high-entropy ceramic powder for the marine diesel engine.
The technical effects of the invention are realized by the following technical scheme:
the high-entropy ceramic powder for the marine diesel engine is used for preparing the high-entropy ceramic coating on the surface of the exhaust valve rod of the marine diesel engine.
The third purpose of the invention is to provide a specific application method of the high-entropy ceramic powder for the marine diesel engine.
The technical effects of the invention are realized by the following technical scheme:
the preparation method of the coating on the surface of the exhaust valve rod of the marine diesel engine, which is provided by the invention, comprises the following operation steps,
s1, cleaning the surface of a substrate to be sprayed;
s2, preparing a transition layer on the surface of the substrate by adopting an atmospheric plasma spraying technology, and preparing the high-entropy ceramic coating for the ship on the surface of the transition layer.
Preferably, the transition layer is a NiCoCrAlY coating.
Preferably, the coating on the surface of the exhaust valve rod of the marine diesel engine is prepared by the following specific method:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base.
S2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1。(HfZrMoNbTi)B2The spraying process parameters are as follows: current 940-; the voltage is 43-47V; argon pressure is 75-85 PSI; helium 50-60 PSI; carrier gas 8-12 PSI; the powder feeding rate is 2-4 r.min-1(ii) a The spraying distance is 60-70 mm; the moving speed of the spray gun is 270-290 mm · s-1。
In conclusion, the invention has the following beneficial effects:
1. by passingThe proportion of each component is adjusted, so that the entropy value of the material is improved. Alloying is generated between the powder by high-energy ball milling in the early stage, boride is generated by reaction between alloy powder and boron powder in partial areas, and then high-entropy alloy boride composite powder obtained by ball milling is further melted and dissolved by plasma sintering, so that high-entropy boride ceramic is finally generated. The method for obtaining the high-entropy ceramic powder by two-step processing gradually increases the content of the high-entropy ceramic in the powder, and finally obtains the pure high-entropy ceramic powder. Hf. The atomic sizes of the five elements of Zr, Mo, Nb and Ti are close and the strong replacement solid solution capacity among the elements greatly improves (HfZrMoNbTi) B2The ability to form. The entropy value of the material is determined by the amount of element types in crystal lattices of the same phase of the material and the molar content of each element, and the high-energy ball milling and the vacuum sintering accelerate the mutual diffusion among the elements to improve the entropy value of the material.
2. Due to (HfZrMoNbTi) B2The ceramic material is a high-temperature-resistant high-entropy ceramic material, and the melting temperature of powder cannot be reached by common thermal spraying, so that a plasma spraying process is selected to prepare a coating. The instantaneous high temperature of the plasma spraying process can enable the high-entropy boride powder to form molten or semi-molten liquid drops and rapidly deposit on the surface of a matrix, and the deposition efficiency and the density of the coating are improved, so that the coating with high hardness and excellent high-temperature resistance is obtained.
3. The average hardness of the existing plasma spraying alloy coating is usually below 10 GPa, while the average hardness of the metal ceramic coating is 10-15 GPa. After the temperature is kept at 900 ℃ for 5 hours, the hardness of the alloy coating and the metal ceramic coating is lower. The high-entropy ceramic coating can effectively improve the surface mechanical property and the high-temperature resistance of the exhaust valve rod. After the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is more than 15 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is more than 1.5 MPa.m1/2。
Drawings
FIG. 1 is a graph showing the hardness of the coating prepared in example 1 after incubation at 900 ℃ for 5 hours.
Detailed Description
To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the high-entropy ceramic powder for marine diesel engine, the application and the application method thereof according to the present invention are as follows.
Example 1
The invention provides high-entropy ceramic powder for a marine diesel engine, which comprises the following components: 5 at.%, Zr: 35 at.%, Mo: 20 at.%, Nb: 20 at.%, Ti: 20 at.%, and the molar ratio of the metal element to the B element is 1: 2.2.
The specific method for preparing the powder comprises the following steps: A1. weighing Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mole percentage, wherein the purity of each element powder is more than 99% and the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, wherein the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the cooling is carried out for 30 min, and the mixing time is 2 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 5 min, grinding the powder and screening to obtain the spraying powder.
The preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the high-entropy ceramic powder for the marine diesel engine, which is prepared by the invention, comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base;
s2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI, carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 950A; the voltage is 45V; argon pressure 80 PSI; helium 55 PSI; carrying 10 PSI gas; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 65 mm; spraying nozzleGun moving speed 280 mm s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 15.5 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 1.6 MPa.m1/2。
FIG. 1 is a hardness curve of the coating prepared in example 1 after the coating is insulated at 900 ℃ for 5 hours, and it can be seen from FIG. 1 that after the high-entropy ceramic coating is insulated at 900 ℃ for 5 hours, the section hardness changes little with the coating thickness, and most hardness data and average hardness are higher than 15 GPa, which is basically consistent with the hardness of the coating before the coating is insulated. Furthermore, the hardness of the high entropy ceramic coatings in all examples was substantially unchanged after heat treatment, which is superior to the hardness of most cermet coatings and alloy coatings after heat treatment, as specified in the comparative examples.
Example 2
The high-entropy ceramic powder for the marine diesel engine comprises the following components of Hf: 20 at.%, Zr: 5 at.%, Mo: 35 at.%, Nb: 20 at.%, Ti: 20 at.%, and the molar ratio of the metal element to the B element is 1: 2.1.
The method for preparing the high-entropy ceramic powder for the marine diesel engine comprises the following steps: A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mol percentage, wherein the purity of each element powder is more than 99 percent, the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 3:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the tank is cooled for 30 min, and the mixing time is 4 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 7 min, grinding the powder and screening to obtain the spraying powder.
The preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the high-entropy ceramic powder for the marine diesel engine, which is prepared by the invention, comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base;
s2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 940A; a voltage of 43V; argon pressure 75 PSI; helium 50 PSI; carrier gas 8 PSI; powder feeding rate of 3 r.min-1(ii) a The spraying distance is 60 mm; moving speed of spray gun is 270 mm s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 16 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 1.8 MPa.m1/2。
Example 3
The high-entropy ceramic powder for the marine diesel engine comprises the following components of Hf: 20 at.%, Zr: 20 at.%, Mo: 5 at.%, Nb: 35 at.%, Ti: 20 at.%, and the molar ratio of the metal element to the B element is 1: 2.5.
The specific method for preparing the high-entropy ceramic powder for the marine diesel engine comprises the following steps: A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mol percentage, wherein the purity of each element powder is more than 99 percent, the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the cooling is carried out for 30 min, and the mixing time is 6 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 10 min, grinding the powder and screening to obtain the spraying powder.
Specifically, the preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the prepared high-entropy ceramic powder for the marine diesel engine comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base.
S2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 960A; a voltage of 47V; argon pressure 85 PSI; helium 60 PSI; carrier gas 12 PSI; powder feeding rate of 4 r.min-1(ii) a The spraying distance is 70 mm; spray gun moving speed 290 mm s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]The ceramic bulletin, 2019, 40(4):530-534.]measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 17 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 2 MPa.m1/2。
Example 4
The high-entropy ceramic powder for the marine diesel engine comprises the following components of Hf: 20 at.%, Zr: 20 at.%, Mo: 20 at.%, Nb: 5 at.%, Ti: 35 at.%, and the molar ratio of metal element to B element is 1: 2.2.
The specific method for preparing the high-entropy ceramic powder for the marine diesel engine comprises the following steps: A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mole percentage, wherein the purity of each element powder is more than 99% and the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, wherein the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the cooling is carried out for 30 min, and the mixing time is 3 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 5-10 min, grinding the powder and screening to obtain the spraying powder.
The preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the prepared high-entropy ceramic powder for the marine diesel engine comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base.
S2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 950A; the voltage is 45V; argon pressure 80 PSI; helium 55 PSI; carrying 10 PSI gas; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 65 mm; spraying nozzleGun moving speed 280 mm s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 15.8 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 2.1 MPa.m1/2。
Example 5
The high-entropy ceramic powder for the marine diesel engine comprises the following components of Hf: 20 at.%, Zr: 20 at.%, Mo: 20 at.%, Nb: 20 at.%, Ti: 20 at.%, and the molar ratio of the metal element to the B element is 1: 2.2.
The specific method for preparing the high-entropy ceramic powder for the marine diesel engine comprises the following steps: A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mol percentage, wherein the purity of each element powder is more than 99 percent, the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the cooling is carried out for 30 min, and the mixing time is 8 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 5-10 min, grinding the powder and screening to obtain the spraying powder.
The preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the prepared high-entropy ceramic powder for the marine diesel engine comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base.
S2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 950A; the voltage is 45V; argon pressure 80 PSI; helium 55 PSI; carrying 10 PSI gas; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 65 mm; the moving speed of the spray gun is 280 mm.s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 17.2 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 1.9 MPa.m1/2。
Example 6
The high-entropy ceramic powder for the marine diesel engine comprises the following components of Hf: 20 at.%, Zr: 20 at.%, Mo: 35 at.%, Nb: 20 at.%, Ti: 5 at.%, and the ratio of metal element to B element is 1: 2.2.
The specific method for preparing the high-entropy ceramic powder for the marine diesel engine comprises the following steps: A1. weighing certain Hf, Zr, Mo, Nb, Ti and B powder according to the high-entropy ceramic components and the mole percentage, wherein the purity of each element powder is more than 99% and the particle size of the powder is 1-5 mu m, putting the powder into a vacuum high-energy ball mill, wherein the ball milling tank is a tungsten carbide lined stainless steel tank, the grinding balls are tungsten carbide grinding balls with the diameter of 10 mm (the ball-powder ratio is approximately equal to 4:1), the ball milling rotation speed is 300 rpm, argon gas is filled into the tank, the pressure is 5 atm, and after ball milling and mixing are carried out for 1 h, the cooling is carried out for 30 min, and the mixing time is 7 h;
A2. and (3) carrying out vacuum (20 Pa) plasma sintering on the obtained mixed powder for 10 min, grinding the powder and screening to obtain the spraying powder.
The preparation method of the high-entropy ceramic coating for improving the surface performance of the exhaust valve rod of the marine diesel engine by using the prepared high-entropy ceramic powder for the marine diesel engine comprises the following steps:
s1, cleaning the surface of a base material by using distilled water, drying for 2 hours in a 100 ℃ forced air drying oven, cleaning the surface of the base by using ethanol, drying for 2 hours in the 100 ℃ forced air drying oven, and finally performing sand blasting on the base.
S2, spraying on the surface of the substrate by adopting an atmospheric plasma spraying technology, wherein the spraying process parameters of the NiCoCrAlY transition layer are as follows: current 710A; a voltage of 34V; argon pressure 65 PSI; helium 115 PSI; carrier gas 45 PSI; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 80 mm; the moving speed of the spray gun is 280 mm.s-1. The parameters of the spraying process of the high-entropy ceramic coating are as follows: current 950A; the voltage is 45V; argon pressure 80 PSI; helium 55 PSI; carrying 10 PSI gas; powder feeding rate of 2 r.min-1(ii) a The spraying distance is 65 mm; the moving speed of the spray gun is 280 mm.s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 17.5 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 1.8 MPa.m1/2。
Comparative example 7:
high-temperature-resistant and wear-resistant CoCrAlYTa-10% Al for ship2O3The coating layer is made of CoCrAlYTa-10% Al produced by FUJIMI of Japan2O3Spraying powder, and preparing CoCrAlYTa-10% Al by supersonic flame spraying technology2O3Coating, the technological parameters are as follows: the oxygen flow rate is 2000 scfh; the kerosene flow rate was 6.5 gph; carrier gas flow 23 scfh; the spraying distance is 370 mm; the rotating speed of the powder feeder is 5 rpm; the moving speed of the spray gun is 280 mm.s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 6.02 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 55.8 MPa.m1/2。
Comparative example 8:
high-temperature-resistant and wear-resistant Cr for ship3C2-NiCr coating, the spraying powder material is Cr3C2-NiCr spray powder, Cr prepared by supersonic flame spraying technique3C2-NiCr coating, process parameters set to: oxygen flow 1900 scfh; the kerosene flow rate was 6 gph; carrier gas flow 23 scfh; the spraying distance is 380 mm; the rotating speed of the powder feeder is 5 rpm; the moving speed of the spray gun is 280 mm.s-1。
An iron-based amorphous/MAX phase composite material for a piston ring and a preparation method and application thereof are disclosed in the specification, CN110205567A [ P ] is]. 2019.]The formula [ J ] is calculated by an indentation method [ Sun Liang Wang Jia Liang, Shixinzheng, a ceramic material fracture toughness indentation method ]]Ceramic bulletin, 2019, 40(4): 530-.]Measuring the fracture toughness of the coating, wherein after the coating is insulated for 5 hours at 900 ℃, the hardness of the coating is 9.32 GPa, the bonding strength is more than 60 MPa, and the fracture toughness is 1.6 MPa.m1/2。
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The high-entropy ceramic powder for the marine diesel engine is characterized in that: the ceramic powder is a high-entropy boride (HfZrMoNbTi) B formed by six elements including Hf, Zr, Mo, Nb, Ti and B2Wherein the mole percentage of Hf, Zr, Mo, Nb and Ti is 5-35%.
2. The high-entropy ceramic powder for marine diesel engines according to claim 1, characterized in that: the molar ratio of the metal element to the B element in the ceramic powder is 1:2.1-1: 2.5.
3. The high-entropy ceramic powder for marine diesel engines according to claim 1, characterized in that: the ceramic powder is prepared by the following operation steps,
A1. weighing metal powder and boron powder according to the mol percentage, putting the metal powder and the boron powder into a vacuum high-energy ball mill, and ball-milling and mixing;
A2. and (3) carrying out vacuum plasma sintering on the powder obtained in the step A1, grinding the powder, and screening to obtain the target product.
4. The high-entropy ceramic powder for marine diesel engines according to claim 3, characterized in that: the powder particle size of the metal powder and the boron powder in the step A1 is 1-5 μm.
5. The high-entropy ceramic powder for marine diesel engines according to claim 3 or 4, characterized in that: and D, ball milling and mixing for 2-8 h in the step A1, and cooling for 30-60 min after mixing for 1-2 h.
6. The high-entropy ceramic powder for the ship as claimed in any one of claims 1 to 4 is applied to the coating of the surface of the exhaust valve rod of the diesel engine for the ship.
7. The application method of the high-entropy ceramic powder for the marine diesel engine according to claim 6, which is used for preparing a coating on the surface of an exhaust valve rod of the marine diesel engine, and is characterized in that: is prepared by the following operation steps of the preparation,
s1, cleaning the surface of a substrate to be sprayed;
s2, preparing a transition layer on the surface of the substrate by adopting an atmospheric plasma spraying technology, and preparing the high-entropy ceramic coating for the ship on the surface of the transition layer.
8. The application method of the high-entropy ceramic powder for the marine diesel engine according to claim 7, characterized in that: the transition layer is a NiCoCrAlY coating.
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