WO2022105029A1 - 一种氮化硼纳米片增强镍基复合涂层及其制备方法 - Google Patents
一种氮化硼纳米片增强镍基复合涂层及其制备方法 Download PDFInfo
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- boron nitride
- nickel
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- nitride nanosheet
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 88
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002135 nanosheet Substances 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 68
- 239000007921 spray Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000011812 mixed powder Substances 0.000 claims abstract description 31
- 238000007750 plasma spraying Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 229940117975 chromium trioxide Drugs 0.000 claims description 21
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 21
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 abstract description 16
- 230000003179 granulation Effects 0.000 abstract description 14
- 238000005469 granulation Methods 0.000 abstract description 14
- 238000005507 spraying Methods 0.000 abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 description 16
- 229920001223 polyethylene glycol Polymers 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 229910001120 nichrome Inorganic materials 0.000 description 14
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000011268 mixed slurry Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 4
- 229910016036 BaF 2 Inorganic materials 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910000601 superalloy Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 using homogenizer Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
Images
Classifications
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Definitions
- the invention belongs to the technical field of coatings, and in particular relates to a boron nitride nanosheet reinforced nickel-based composite coating and a preparation method thereof.
- Aerospace, petrochemical metallurgy, energy power, marine engineering and other major national high-tech equipment have a large number of key metal friction moving parts that are related to equipment service safety. Under extremely harsh service conditions such as oxidation, corrosion, etc., the service life of parts is reduced due to strong friction and wear, which in turn affects the reliability and service life of the entire equipment. Typically, the failure of kinematic components begins at their surface. Therefore, while maintaining the inherent comprehensive characteristics (toughness, strength, etc.) of the base material of the parts, the use of surface engineering technology to prepare a wear-resistant composite coating on the surface of the moving parts is recognized as an economical and feasible solution to the above problems. Useful ways.
- NiCr alloy coating has excellent corrosion resistance, wear resistance, high temperature oxidation resistance and good compatibility with substrate and coating materials, but its mechanical properties are poor.
- Cr 2 O 3 ceramic coating has the properties of high strength, wear resistance, corrosion resistance and high temperature oxidation resistance, but its brittleness is high and its compatibility with the substrate is poor, and the prepared coating often has defects such as cracks and holes , which restricts the application of ceramic coatings. Therefore, using NiCr/Cr 2 O 3 to prepare a nickel-based composite coating on the surface of the substrate can improve the service life of parts.
- PS304 plasma spraying developed by NASA by adding BaF 2 , CaF 2 eutectic and soft metal Ag into NiCr/Cr 2 O 3 as composite lubricants realizes the plasma spray coating from room temperature to High temperature (800 °C) continuous lubrication, effectively prevent the wear between the paired materials during the friction process.
- the patent CN102041466A (a high-performance high-temperature solid self-lubricating coating and its preparation method) preparation method first separately ultrasonically atomizes NiCr alloy powder, Cr 2 O 3 powder, Ag powder and eutectic BaF 2 /CaF 2 powder. Mechanical mixing is carried out, followed by atmospheric plasma spraying to obtain a high-temperature self-lubricating and wear-resistant composite coating.
- the effective service temperature of the coating is lower than 800°C, which cannot meet the long-term service of key moving parts in harsher environments.
- the self-lubricating performance of the coating is reduced due to the consumption of thermal diffusion of the soft metal Ag, and the effective self-lubricating temperature of the eutectic BaF 2 ⁇ CaF 2 fluoride is higher than 600°C, which cannot effectively compensate for the loss of Ag, resulting in the decline of the lubricating performance at medium and low temperature.
- there are too many components in this series of coatings and the difference in the density of each component easily leads to different deposition efficiencies of powders during thermal spraying, and the addition of lubricants reduces the mechanical properties of the coatings.
- the purpose of the present invention is to provide a boron nitride nanosheet reinforced nickel-based composite coating and a preparation method thereof, and the nickel-based composite material provided by the present invention has good performance.
- the invention provides a preparation method of boron nitride nanosheet reinforced nickel-based composite coating, comprising:
- the powder is spray granulated to obtain a spray feed
- Plasma spraying is performed on the sprayed feed material to obtain a boron nitride nanosheet reinforced nickel-based composite coating.
- the preparation method of the mixed powder includes:
- the slurry is dried and then ground to obtain a mixed powder
- the ratio of the balls in the ball milling process is (3-5):1, the rotational speed is 200-400 r/min, and the ball-milling time is 5-7 hours;
- the drying temperature is 70-90°C.
- the mass ratio of the nickel powder, the chromium powder and the chromium trioxide powder is (55-65):(10-20):(20-30).
- the preparation method of the boron nitride nanosheet dispersion comprises:
- the ultrasonic dispersion time is 3 to 5 hours.
- the method for mixing the mixed powder and the boron nitride nanosheet dispersion includes:
- the rotational speed in the stirring and dispersing process is 4500-5500 rpm, and the stirring and dispersing time is 4-6 hours.
- the temperature for drying after mixing the mixed powder and the boron nitride nanosheet dispersion liquid is 70-90°C.
- the mass content of the boron nitride nanosheets in the powder is 0.5-1.5%.
- the current in the plasma spraying process is 750-850A
- the voltage is 35-45V
- the main gas argon flow is 30-40 slm
- the auxiliary gas helium flow is 30-40 slm.
- the distance between the nozzle and the sprayed substrate is 70-90 mm.
- the invention provides a new boron nitride nano-sheet reinforced nickel-based composite coating material system, namely boron nitride nano-sheet (Boron Nitride Nanoplatelet, BNNP) reinforced (NiCr/Cr 2 O 3 , NCCO) nickel-based high temperature composite coating, and using nickel powder, chromium powder, chromium trioxide powder, boron nitride nanosheets as the original powder, using homogenizer, spray granulation to prepare plasma spray feed, and plasma spray technology to prepare composite coating, Improve the mechanical properties of composite coatings, and develop a BNNP/NCCO composite coating material system with both excellent high temperature tribological properties and good high temperature oxidation resistance.
- the properties of the layered structure coatings prepared by plasma spraying are mainly affected by the morphology, strength, crystal structure of the flat particles, and the bonding strength between the flat particles and between the flat particles and the substrate.
- the invention provides a method for preparing a boron nitride nano-sheet reinforced NiCr/Cr 2 O 3 composite coating with both light weight, high strength and toughness and lubricating properties, that is, using a homogenizer dispersion combined with a spray granulation technology to prepare a spray feed Then, the obtained powder is sintered by plasma spraying technology to prepare a composite coating, and a new composite coating with various excellent properties such as high temperature resistance, wear resistance, corrosion resistance and low friction coefficient is obtained.
- the present invention provides a boron nitride nanosheet reinforced nickel-based composite coating prepared by the method described in the above technical solution.
- NiCr with excellent oxidation resistance, corrosion resistance and good compatibility with nickel-based superalloys and coating materials is selected as the matrix phase, and Cr 2 O 3 is used as the reinforcing phase to improve the wear resistance of the coating.
- BNNP as the self-lubricating phase, a new type of composite coating with high temperature resistance, wear resistance, corrosion resistance, low friction coefficient and other excellent properties was prepared by plasma spraying technology.
- FIG. 1 is a process flow diagram of a method for preparing a boron nitride nanosheet reinforced nickel-based composite coating provided by the present invention
- Fig. 2 is the SEM image of the plasma spraying feed material prepared in Example 1 of the present invention.
- Fig. 3 is the Raman spectrogram of the BNNP used in the preparation process of the embodiment of the present invention 1 and the plasma spraying feed;
- Fig. 4 is the XRD diffraction pattern of the nickel-based composite coating prepared by the embodiment of the present invention and the comparative example;
- Fig. 5 is the SEM image of the section of the boron nitride nanosheet reinforced nickel-based composite coating prepared in Example 1 of the present invention
- Fig. 6 is the hardness performance of the nickel-based composite coating prepared by the embodiment of the present invention and the comparative example
- Fig. 7 is the friction coefficient detection result of the nickel-based composite layer prepared by the embodiment of the present invention and the comparative example;
- Fig. 8 is the friction coefficient detection result of the nickel-based composite layer prepared by the embodiment of the present invention and the comparative example;
- FIG. 9 is the detection result of the wear amount of the nickel-based composite layers prepared in the embodiment of the present invention and the comparative example.
- the present invention provides a method for preparing a boron nitride nanosheet reinforced nickel-based composite coating, the process flow chart of which is shown in FIG. 1 , and the preparation method of the boron nitride nanosheet reinforced nickel-based composite coating includes:
- the powder is spray granulated to obtain a spray feed
- Plasma spraying is performed on the sprayed feed material to obtain a boron nitride nanosheet reinforced nickel-based composite coating.
- the preparation method of the mixed powder preferably comprises:
- the slurry is dried and then ground to obtain a mixed powder.
- the equipment of the ball milling is preferably a horizontal planetary ball mill, and the ratio of the ball material in the ball milling process is preferably (3-5): 1, more preferably 4: 1, and the ball mill in the ball milling process
- the rotation speed is preferably 200-400 r/min, more preferably 250-350 r/min, most preferably 300 r/min, and the ball milling time is preferably 5-7 hours, more preferably 6 hours.
- the drying temperature is preferably 70 to 90°C, more preferably 80°C.
- the mass ratio of the nickel powder, the chromium powder and the chromium trioxide powder is preferably (55-65):(10-20):(20-30), more preferably 60:15:25.
- the preparation method of the boron nitride nanosheet dispersion preferably includes:
- the boron nitride nanosheets and isopropanol are mixed for ultrasonic dispersion to obtain a boron nitride nanosheet dispersion.
- the ultrasonic dispersion time is preferably 3 to 5 hours, more preferably 4 hours.
- the thickness of the boron nitride nanosheets is preferably ⁇ 30 nm, and the diameter is preferably ⁇ 5 ⁇ m.
- the present invention has no special limitation on the source of the boron nitride nanosheets. Boron nitride well-known to those skilled in the art is used.
- Nanosheets can be purchased from the market; boron nitride nanosheets (BN nanoplatelets, BNNP) have a two-dimensional structure, excellent mechanical properties (elastic modulus 700-900GPa, yield strength-35GPa), good thermal conductivity 300W/mK, low density (2.1g/cm 3 ) and excellent high temperature stability (still maintains a stable structure in the atmospheric environment ⁇ 1000 °C), these excellent properties make BNNP a great potential for self-lubricating composite materials in a wide temperature range
- the reinforced phase can not only improve the mechanical properties of the composites, but also make the composites have excellent self-lubricating properties in a wide temperature range.
- the method for mixing the mixed powder and the boron nitride nanosheet dispersion preferably includes:
- the mixed powder is put into the boron nitride nanosheet dispersion liquid for stirring and dispersion.
- a homogenizer is preferably used for the stirring and dispersing, the rotational speed in the stirring and dispersing process is preferably 4500-5500 rpm, more preferably 5000 rpm, and the stirring and dispersing time is preferably 4-6 hours, more preferably 5 hours.
- drying after mixing the mixed powder and boron nitride nanosheet dispersion is preferably performed in a vacuum drying oven, and the drying temperature is preferably 70-90°C, more preferably 80°C; the drying is completed Then, the obtained dry powder is preferably ground to obtain a powder.
- the mass content of the boron nitride nanosheets in the boron nitride nanosheet dispersion liquid in the powder is preferably 0.5-1.5%, more preferably 0.8-1.2%, and most preferably 1%.
- the present invention has no special restrictions on the spray granulation, and the spray granulation technology well-known to those skilled in the art can be used. is 2100-2200 rpm; the nozzle inlet temperature is preferably 260-280°C, more preferably 270°C; the nozzle outlet temperature is preferably 110-120°C.
- the spray granulation preferably comprises:
- the slurry is spray granulated to obtain a spray feed.
- the polyethylene glycol solution is preferably an aqueous solution of polyethylene glycol, and the mass concentration of the polyethylene glycol solution is preferably 8-12%;
- the mass ratio is preferably (43-47):(43-47):(9-11).
- the current in the plasma spraying process is preferably 750-850A, more preferably 780-820A, and most preferably 800A; the voltage is preferably 35-45V, more preferably 38-42V, and most preferably 40V,
- the flow rate of the main gas argon is preferably 30-40slm, more preferably 35slm, the flow rate of the auxiliary gas helium is preferably 30-40slm, more preferably 35slm, and the distance between the nozzle and the spray substrate in the plasma spraying process is preferably 70-90mm, more preferably It is 75 to 85 mm, most preferably 80 mm.
- the present invention provides a boron nitride nanosheet reinforced nickel-based composite coating prepared by the method described in the above technical solution.
- the invention provides a new boron nitride nanosheet reinforced nickel-based composite coating material system, namely boron nitride nanosheets (BNNP) reinforced (NiCr/Cr 2 O 3 , NCCO) nickel-based high temperature composite coating, and using nickel powder, chromium powder, chromium trioxide powder, boron nitride nanosheets as the original powder, using homogenizer, spray granulation to prepare plasma spray feed, and plasma spray technology to prepare composite coating, Improve the mechanical properties of composite coatings, and develop a BNNP/NCCO composite coating material system with both excellent high temperature tribological properties and good high temperature oxidation resistance.
- BNNP boron nitride nanosheets
- NCCO boron nitride nanosheets
- the properties of the layered structure coatings prepared by plasma spraying are mainly affected by the morphology, strength, crystal structure of the flat particles, and the bonding strength between the flat particles and between the flat particles and the substrate.
- the invention provides a method for preparing a boron nitride nano-sheet reinforced NiCr/Cr 2 O 3 composite coating with both light weight, high strength and toughness and lubricating properties, that is, using a homogenizer dispersion combined with a spray granulation technology to prepare a spray feed Then, the obtained powder is sintered by plasma spraying technology to prepare a composite coating, and a new composite coating with high strength, wear resistance, low friction coefficient and other excellent properties is obtained.
- NiCr with excellent oxidation resistance, corrosion resistance and good compatibility with nickel-based superalloys and coating materials is selected as the matrix phase, and Cr 2 O 3 is used as the reinforcing phase to improve the wear resistance of the coating.
- BNNP as the self-lubricating phase, a new type of composite coating with high temperature resistance, wear resistance, corrosion resistance, low friction coefficient and other excellent properties was prepared by plasma spraying technology.
- the nickel powder used in the following examples of the present invention is provided by Shanghai Yaotian New Material Technology Co., Ltd.
- the chromium powder is provided by Shanghai Yaotian New Material Technology Co., Ltd.
- the chromium trioxide powder is provided by Shanghai Yaotian New Material Technology Co., Ltd.
- the boron nitride nanosheets were provided by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.
- nickel powder, chromium powder and chromium trioxide powder into a horizontal planetary ball mill, add isopropyl alcohol for ball milling, the ratio of ball to material in the ball milling process is 4:1, the rotational speed of the ball mill is 300 r/min, and the ball is milled for 6 hours to obtain mixed slurry;
- the above mixed slurry is dried in a vacuum drying oven at 80°C, and then ground into powder to obtain a mixed powder;
- the above mixed powder is sprayed and granulated to obtain spherical plasma spray feed
- the above-mentioned plasma spraying feeding material is plasma sprayed, the current is 800A, the voltage is 40V, the main gas argon flow rate is 35slm, the auxiliary gas helium gas flow rate is 35slm, and the distance between the plasma spray nozzle and the spray substrate is 80mm to obtain a nickel-based composite coating.
- nickel powder, chromium powder and chromium trioxide powder into a horizontal planetary ball mill, add isopropyl alcohol for ball milling, the ratio of ball to material in the ball milling process is 4:1, the rotational speed of the ball mill is 300 r/min, and the ball is milled for 6 hours to obtain mixed slurry;
- the above mixed slurry is dried in a vacuum drying oven at 80°C, and then ground into powder to obtain a mixed powder;
- the boron nitride nanosheets were placed in isopropanol for ultrasonic dispersion for 4 hours to obtain a boron nitride nanosheet dispersion;
- the mixed powder into the boron nitride nanosheet dispersion liquid, stir and disperse with a homogenizer, the rotation speed is 5000 rpm, and the time is 5 hours, and the obtained mixed liquid is dried in a vacuum drying box at 80° C. powder to obtain powder, and the mass content of boron nitride nanosheets in the powder is 0.5%;
- Polyethylene glycol is dissolved in water, and the mass fraction of polyethylene glycol in water is 10 wt % to obtain a polyethylene glycol solution; the above-mentioned powder, water and polyethylene glycol solution are in a mass fraction ratio of 45:45: 10 Mixing to obtain a slurry; spraying and granulating the obtained slurry, the nozzle rotation speed is 2100rpm, the nozzle inlet temperature is 270°C, and the outlet temperature is 115°C to obtain spherical plasma spray feed;
- the above-mentioned plasma spraying feeding material is plasma sprayed, the current is 800A, the voltage is 40V, the main gas argon gas flow rate is 35slm, the auxiliary gas helium gas flow rate is 35slm, and the distance between the plasma spray nozzle and the spray substrate is 90mm, to obtain boron nitride nanosheets reinforced nickel base Composite coating.
- nickel powder, chromium powder and chromium trioxide powder into a horizontal planetary ball mill, add isopropyl alcohol for ball milling, the ratio of ball to material in the ball milling process is 4:1, the rotational speed of the ball mill is 300 r/min, and the ball is milled for 6 hours to obtain mixed slurry;
- the above mixed slurry is dried in a vacuum drying oven at 80°C, and then ground into powder to obtain a mixed powder;
- the boron nitride nanosheets were placed in isopropanol for ultrasonic dispersion for 4 hours to obtain a boron nitride nanosheet dispersion;
- the mixed powder into the boron nitride nanosheet dispersion liquid, stir and disperse with a homogenizer, the rotation speed is 5000 rpm, and the time is 5 hours, and the obtained mixed liquid is dried in a vacuum drying box at 80° C. powder to obtain powder, and the mass content of boron nitride nanosheets in the powder is 1%;
- Polyethylene glycol is dissolved in water, and the mass fraction of polyethylene glycol in water is 10 wt % to obtain a polyethylene glycol solution; the above-mentioned powder, water and polyethylene glycol solution are in a mass fraction ratio of 45:45: 10 Mixing to obtain a slurry; spray granulation of the obtained slurry, the nozzle rotation speed is 2100rpm, the nozzle inlet temperature is 270°C, and the outlet temperature is 115°C to obtain spherical plasma spray feed;
- the above-mentioned plasma spraying feeding material is plasma sprayed, the current is 800A, the voltage is 40V, the main gas argon gas flow rate is 35slm, the auxiliary gas helium gas flow rate is 35slm, and the distance between the plasma spray nozzle and the spray substrate is 90mm, to obtain boron nitride nanosheets reinforced nickel base Composite coating.
- nickel powder, chromium powder and chromium trioxide powder into a horizontal planetary ball mill, add isopropyl alcohol for ball milling, the ratio of ball to material in the ball milling process is 4:1, the rotational speed of the ball mill is 300 r/min, and the ball is milled for 6 hours to obtain mixed slurry;
- the above mixed slurry is dried in a vacuum drying oven at 80°C, and then ground into powder to obtain a mixed powder;
- the boron nitride nanosheets were placed in isopropanol for ultrasonic dispersion for 4 hours to obtain a boron nitride nanosheet dispersion;
- the mixed powder into the boron nitride nanosheet dispersion liquid, stir and disperse with a homogenizer, the rotation speed is 5000 rpm, and the time is 5 hours, and the obtained mixed liquid is dried in a vacuum drying box at 80° C. powder to obtain powder, and the mass content of boron nitride nanosheets in the powder is 1.5%;
- Polyethylene glycol is dissolved in water, and the mass fraction of polyethylene glycol in water is 10 wt % to obtain a polyethylene glycol solution; the above-mentioned powder, water and polyethylene glycol solution are in a mass fraction ratio of 45:45: 10 Mixing to obtain a slurry; spray granulation of the obtained slurry, the nozzle rotation speed is 2100rpm, the nozzle inlet temperature is 270°C, and the outlet temperature is 115°C to obtain spherical plasma spray feed;
- the above-mentioned plasma spraying feeding material is plasma sprayed, the current is 800A, the voltage is 40V, the main gas argon gas flow rate is 35slm, the auxiliary gas helium gas flow rate is 35slm, and the distance between the plasma spray nozzle and the spray substrate is 90mm, to obtain boron nitride nanosheets reinforced nickel base Composite coating.
- Example 2 The plasma spraying feedstock prepared in Example 1 of the present invention was tested by SEM, and the test results are shown in Figure 2. It can be seen from Figure 2(a) that the powder has good sphericity and uniform size distribution; from Figure 2(b), it can be seen that less Layers of boron nitride nanosheets are uniformly dispersed in the powder.
- Example 3 The original BNNP used in Example 1 and the prepared plasma spraying feed were subjected to Raman (Raman spectroscopy) detection. The detection results are shown in Figure 3. It can be seen from Figure 3 that compared with the original BNNP, the plasma sprayed feed detected G The peaks were blue-shifted (right-shifted), and the half-peak width became larger, which indicated that the pristine boron nitride nanosheets could be thinned and uniformly dispersed in the powder after dispersion and spray granulation.
- the nickel-based composite coatings prepared in the embodiments of the present invention and the comparative examples were subjected to XRD detection, and the detection results are shown in Figure 4. It can be seen from Figure 4 that the nickel-based composite coatings mainly include ⁇ -NiCr, Cr 2 O 3 and a small amount of NiO .
- the hardness of the nickel-based composite coatings prepared in the embodiments of the present invention and the comparative examples was tested, and the coatings were measured by a microhardness tester (XD-1000TMC/LCD, Shanghai Taiming Optical Instrument Co., Ltd.) without adding boron nitride nanosheets and adding
- the hardness of boron nitride nanosheets with the content of 0.5wt.%, 1.0wt.% and 1.5wt.% are 548HV 0.2 , 609HV 0.2 , 620HV 0.2 and 575HV 0.2 respectively, as shown in Figure 6, it can be seen that adding 1.5wt.
- the hardness of the boron nitride nanosheet reinforced nickel-based composite coating with % boron nitride nanosheets decreases slightly, which may be mainly due to the inevitable agglomeration of boron nitride nanosheets, which will lead to the formation of holes in the coating and affect its density. , resulting in a decrease in hardness.
- the composite coatings prepared in Examples 1 to 3 of the present invention and Comparative Example 1 were subjected to friction and wear tests.
- the friction and wear tester (HT1000, Lanzhou Zhongke Kaihua Technology Development Co., Ltd.) was used at a load of 20N, a rotational speed of 300rpm and 1200rpm, and a rotation radius of 20N.
- the friction coefficient and wear amount of the coating obtained by measuring the 2mm and 4mm diameter alumina balls are shown in Figure 7 (rotation speed 300rpm), Figure 8 (rotation speed 1200rpm) and Figure 9, it can be seen that with the increase of boron nitride With the increase of nanosheets, the wear resistance and antifriction properties of the coating are improved.
- the invention provides a new boron nitride nano-sheet reinforced nickel-based composite coating material system, namely boron nitride nano-sheet (Boron Nitride Nanoplatelet, BNNP) reinforced (NiCr/Cr 2 O 3 , NCCO) nickel-based high temperature composite coating, and using nickel powder, chromium powder, chromium trioxide powder, boron nitride nanosheets as the original powder, using homogenizer, spray granulation to prepare plasma spray feed, and plasma spray technology to prepare composite coating, Improve the mechanical properties of composite coatings, and develop a BNNP/NCCO composite coating material system with both excellent high temperature tribological properties and good high temperature oxidation resistance.
- the invention provides a method for preparing a boron nitride nano-sheet reinforced NiCr/Cr 2 O 3 composite coating with both light weight, high strength and toughness and lubricating properties, that is, using a homogenizer dispersion combined with a spray granulation technology to prepare a spray feed Then, the obtained powder is sintered by plasma spraying technology to prepare a composite coating, and a new composite coating with high strength, wear resistance, low friction coefficient and other excellent properties is obtained.
- NiCr with excellent oxidation resistance, corrosion resistance and good compatibility with nickel-based superalloys and coating materials is selected as the matrix phase, and Cr 2 O 3 is used as the reinforcing phase to improve the wear resistance of the coating.
- BNNP as the self-lubricating phase, a new type of composite coating with high temperature resistance, wear resistance, corrosion resistance, low friction coefficient and other excellent properties was prepared by plasma spraying technology.
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Abstract
一种氮化硼纳米片增强镍基复合涂层及其制备方法,包括:将镍粉、铬粉和三氧化二铬粉混合,得到混合粉末;将所述混合粉末和氮化硼纳米片分散液混合后干燥,得到粉体;将所述粉体进行喷雾造粒,得到喷涂喂料;将所述喷涂喂料进行等离子喷涂,得到氮化硼纳米片增强镍基复合涂层。以镍粉,铬粉,三氧化二铬粉,氮化硼纳米片为原始粉末,采用均质机,喷雾造粒制备等离子喷涂喂料,以及等离子喷涂技术制备复合涂层,可以提高复合涂层的力学性能,得到兼备优异的力学性能和摩擦学性能的复合涂层材料体系。
Description
本申请要求于2020年11月23日提交中国专利局、申请号为202011322484.3、发明名称为“一种氮化硼纳米片增强镍基复合涂层及其制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本发明属于涂层技术领域,尤其涉及一种氮化硼纳米片增强镍基复合涂层及其制备方法。
航空航天、石化冶金、能源动力、海洋工程等国家重大高新技术装备中存在有大量事关装备服役安全的关键金属摩擦运动副零部件,其在高/低温(宽温域)、高速、重载、氧化、腐蚀等极端恶劣服役条件下承受强烈摩擦磨损而导致零部件的使役寿命的降低,进而影响整个装备的可靠性和寿命。通常情况下,运动副零部件的失效始于它们的表面。因此,在保持零部件基体材料固有的综合特性(韧性、强度等)的同时,采用表面工程技术在运动副零部件表面制备耐磨复合涂层,被公认是解决上述问题即经济又切实可行的有效方法。
NiCr合金涂层具有较为优异的耐腐蚀、耐磨损、耐高温氧化且与基体以及涂层材料均有良好相容性,但其力学性能较差。Cr
2O
3陶瓷涂层具有高强度,耐磨损,耐腐蚀和耐高温氧化的性能,但其脆性较高,与基体相容性较差,制备出的涂层经常出现裂纹、孔洞等缺陷,制约了陶瓷涂层的应用。因此,选用NiCr/Cr
2O
3在基体表面制备一种镍基复合涂层可以提高零部件的使役寿命。美国国家航空航天局(NASA)研发的PS304(plasma spraying)通过在NiCr/Cr
2O
3内添加BaF
2、CaF
2共晶和软金属Ag为复合润滑剂,实现了等离子喷涂涂层从室温到高温(800℃)连续润滑,有效的防止摩擦过程中对偶材料之间磨损。专利CN102041466A(一种高性能高温固体自润滑涂层及其制备方法)制备方法首先分别将NiCr合金粉末、Cr
2O
3粉末、Ag粉末和共熔物BaF
2/CaF
2粉末超声气体雾化后进行机械混合,之后进行大气等离子喷涂得到高温自润滑耐磨复合涂层。但是,该涂层的有效服役温度低于800℃,不能满足现在关键运动 副零部件在更为苛刻环境下长时期的服役。而软金属Ag由于热扩散的消耗降低的涂层自润滑性能,共晶BaF
2·CaF
2氟化物有效自润滑温度高于600℃,不能有效弥补Ag的流失导致中低温的润滑性能下降。此外,该系列涂层成分过多,各组元密度的差异易导致粉体在热喷涂过程中存在不同沉积效率,以及润滑剂的添加降低了涂层的力学性能。
发明内容
有鉴于此,本发明的目的在于提供一种氮化硼纳米片增强镍基复合涂层及其制备方法,本发明提供的镍基复合材料具有较好的性能。
本发明提供了一种氮化硼纳米片增强镍基复合涂层的制备方法,包括:
将镍粉、铬粉和三氧化二铬粉混合,得到混合粉末;
将所述混合粉末和氮化硼纳米片分散液混合后干燥,得到粉体;
将所述粉体进行喷雾造粒,得到喷涂喂料;
将所述喷涂喂料进行等离子喷涂,得到氮化硼纳米片增强镍基复合涂层。
优选的,所述混合粉末的制备方法包括:
将镍粉、铬粉和三氧化二铬粉用异丙醇进行球磨,得到浆料;
将所述浆料进行干燥后研磨,得到混合粉末;
所述球磨过程中的球料比例为(3~5):1,转速为200~400r/min,球磨时间为5~7小时;
所述干燥的温度为70~90℃。
优选的,所述镍粉、铬粉和三氧化二铬粉的质量比为(55~65):(10~20):(20~30)。
优选的,所述氮化硼纳米片分散液的制备方法包括:
将氮化硼纳米片和异丙醇混合进行超声分散,得到氮化硼纳米片分散液;
所述超声分散的时间为3~5小时。
优选的,所述混合粉末和氮化硼纳米片分散液混合的方法包括:
将混合粉末放入氮化硼纳米片分散液中进行搅拌分散;
所述搅拌分散过程中的转速为4500~5500rpm,所述搅拌分散的时间为4~6小时。
优选的,所述混合粉末和氮化硼纳米片分散液混合后干燥的温度为70~90℃。
优选的,所述氮化硼纳米片在粉体中的质量含量为0.5~1.5%。
优选的,所述等离子喷涂过程中的电流为750~850A,电压为35~45V,主气氩气流量为30~40slm,辅气氦气流量为30~40slm。
优选的,所述等离子喷涂过程中喷嘴距离喷涂基体的距离为70~90mm。
本发明提供了一种新的氮化硼纳米片增强镍基复合涂层材料体系,即氮化硼纳米片(Boron Nitride Nanoplatelet,BNNP)增强的(NiCr/Cr
2O
3,NCCO)镍基高温复合涂层,并以镍粉,铬粉,三氧化二铬粉,氮化硼纳米片为原始粉末,采用均质机,喷雾造粒制备等离子喷涂喂料,以及等离子喷涂技术制备复合涂层,提高复合涂层的力学性能,发展兼备优异的高温摩擦学性能和良好高温抗氧化性能的BNNP/NCCO复合涂层材料体系。
等离子喷涂制备的层状结构涂层的性能主要受到扁平粒子形貌、强度、晶体结构和扁平粒子间及扁平粒子与基体结合强度的影响。本发明提供了一种兼具轻质、高强韧性和润滑性能的氮化硼纳米片增强NiCr/Cr
2O
3复合涂层的制备方法,即采用均质机分散结合喷雾造粒技术制备喷涂喂料,然后将得到的粉末利用等离子喷涂技术烧结制备复合涂层,获得兼备耐高温、耐磨损、耐腐蚀、低摩擦系数等多种优异性能配合的新型复合涂层。
本发明提供了一种上述技术方案所述的方法制备得到的氮化硼纳米片增强镍基复合涂层。
本发明选择具有较优异的抗氧化性能、耐腐蚀性能且与镍基高温合金以及涂层材料均有良好相容性的NiCr为基体相,以Cr
2O
3作为增强相提升涂层的耐磨性能,以BNNP作为自润滑相,采用等离子喷涂技术制备出具有耐高温、耐磨损、耐腐蚀、低摩擦系数等多种优异性能配合的新型复合涂层。
图1为本发明提供的氮化硼纳米片增强镍基复合涂层制备方法的工艺流程图;
图2为本发明实施例1制备的等离子喷涂喂料的SEM图;
图3为本发明实施例1制备过程中的使用的BNNP以及等离子喷涂喂料的拉曼光谱图;
图4为本发明实施例和比较例制备的镍基复合涂层的XRD衍射图谱;
图5为本发明实施例1制备的氮化硼纳米片增强镍基复合涂层断面的SEM图;
图6为本发明实施例和比较例制备的镍基复合涂层的硬度性能;
图7为本发明实施例和比较例制备的镍基复合图层的摩擦系数检测结果;
图8为本发明实施例和比较例制备的镍基复合图层的摩擦系数检测结果;
图9为本发明实施例和比较例制备的镍基复合图层的磨损量检测结果。
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员经改进或润饰的所有其它实例,都属于本发明保护的范围。应理解,本发明实施例仅用于说明本发明的技术效果,而非用于限制本发明的保护范围。实施例中,所用方法如无特别说明,均为常规方法。
本发明提供了一种氮化硼纳米片增强镍基复合涂层的制备方法,其工艺流程图如图1所示,所述氮化硼纳米片增强镍基复合涂层的制备方法包括:
将镍粉、铬粉和三氧化二铬粉混合,得到混合粉末;
将所述混合粉末和氮化硼纳米片分散液混合后干燥,得到粉体;
将所述粉体进行喷雾造粒,得到喷涂喂料;
将所述喷涂喂料进行等离子喷涂,得到氮化硼纳米片增强镍基复合涂层。
在本发明中,所述混合粉末的制备方法优选包括:
将镍粉、铬粉和三氧化二铬粉用异丙醇进行球磨,得到浆料;
将所述浆料进行干燥后研磨,得到混合粉末。
在本发明中,所述球磨的设备优选为卧式行星球磨机,所述球磨过程中的球料比例优选为(3~5):1,更优选为4:1,所述球磨过程中球磨机的转速优选为200~400r/min,更优选为250~350r/min,最优选为300r/min,所述球磨的时间优选为5~7小时,更优选为6小时。
在本发明中,所述干燥的温度优选为70~90℃,更优选为80℃。
在本发明中,所述镍粉、铬粉和三氧化二铬粉的质量比优选为(55~65):(10~20):(20~30),更优选为60:15:25。
在本发明中,所述氮化硼纳米片分散液的制备方法优选包括:
将氮化硼纳米片和异丙醇混合进行超声分散,得到氮化硼纳米片分散液。
在本发明中,所述超声分散的时间优选为3~5小时,更优选为4小时。
在本发明中,所述氮化硼纳米片的厚度优选≤30nm,直径优选≤5μm,本发明对所述氮化硼纳米片的来源没有特殊的限制,采用本领域技术人员熟知的氮化硼纳米片即可,可由市场购买获得;氮化硼纳米片(BN nanoplatelet,BNNP)具有二维结构,具有优异的力学性能(弹性模量700~900GPa、屈服强度~35GPa)、良好的热导性能300W/mK、低的密度(2.1g/cm
3)和优异的高温稳定性能(大气环境下~1000℃仍保持稳定结构),这些优异性能使BNNP成为宽温域自润滑复合材料中极具潜力的增强相,不仅能够提高复合材料的力学性能,同时能使得复合材料具有优异的宽温域自润滑性能。
在本发明中,所述混合粉末和氮化硼纳米片分散液混合的方法优选包括:
将混合粉末放入氮化硼纳米片分散液中进行搅拌分散。
在本发明中,所述搅拌分散优选采用均质机,所述搅拌分散过程中的转速优选为4500~5500rpm,更优选为5000rpm,所述搅拌分散的时间优选为4~6小时,更优选为5小时。
在本发明中,所述混合粉末和氮化硼纳米片分散液混合后干燥优选在真空干燥箱中进行,所述干燥的温度优选为70~90℃,更优选为80℃;所述干燥完成后优选将得到的干燥粉末研磨,得到粉体。
在本发明中,所述氮化硼纳米片分散液中的氮化硼纳米片在粉体中的质量含量优选为0.5~1.5%,更优选为0.8~1.2%,最优选为1%。
本发明对所述喷雾造粒没有特殊的限制,采用本领域技术人员熟知的喷雾造粒技术即可,在本发明中,所述喷雾造粒过程中的喷嘴转速优选为2000~2500rpm,更优选为2100~2200rpm;喷嘴进口温度优选为260~280℃,更优选为270℃;喷嘴出口温度优选为110~120℃。在本发明中,所述喷雾造粒优选包括:
将所述粉体、聚乙二醇溶液和水混合,得到浆料;
将所述浆料进行喷雾造粒,得到喷涂喂料。
在本发明中,所述聚乙二醇溶液优选为聚乙二醇水溶液,所述聚乙二醇溶液的质量浓度优选为8~12%;所述粉体、水和聚乙二醇溶液的质量比优选为(43~47):(43~47):(9~11)。
在本发明中,所述等离子喷涂过程中的电流优选为750~850A,更优选为780~820A,最优选为800A;电压优选为35~45V,更优选为38~42V,最优选为40V,主气氩气流量优选为30~40slm,更优选为35slm,辅气氦气流量优选为30~40slm,更优选为35slm,等离子喷涂过程中喷嘴距离喷涂基体的距离优选为70~90mm,更优选为75~85mm,最优选为80mm。
本发明提供了一种上述技术方案所述的方法制备得到的氮化硼纳米片增强镍基复合涂层。
本发明提供了一种新的氮化硼纳米片增强镍基复合涂层材料体系,即氮化硼纳米片(Boron Nitride Nanosheets,BNNP)增强的(NiCr/Cr
2O
3,NCCO)镍基高温复合涂层,并以镍粉,铬粉,三氧化二铬粉,氮化硼纳米片为原始粉末,采用均质机,喷雾造粒制备等离子喷涂喂料,以及等离子喷涂技术制备复合涂层,提高复合涂层的力学性能,发展兼备优异的高温摩擦学性能和良好高温抗氧化性能的BNNP/NCCO复合涂层材料体系。
等离子喷涂制备的层状结构涂层的性能主要受到扁平粒子形貌、强度、晶体结构和扁平粒子间及扁平粒子与基体结合强度的影响。本发明提供了一种兼具轻质、高强韧性和润滑性能的氮化硼纳米片增强NiCr/Cr
2O
3复合涂层的制备方法,即采用均质机分散结合喷雾造粒技术制备喷涂喂料,然后将得到的粉末利用等离子喷涂技术烧结制备复合涂层,获得兼备高强度、耐磨损、低摩擦系数等多种优异性能配合的新型复合涂层。
本发明选择具有较优异的抗氧化性能、耐腐蚀性能且与镍基高温合金以及涂层材料均有良好相容性的NiCr为基体相,以Cr
2O
3作为增强相提升涂层的耐磨性能,以BNNP作为自润滑相,采用等离子喷涂技术制备出具有耐高温、耐磨损、耐腐蚀、低摩擦系数等多种优异性能配合的新型复合涂层。
本发明以下实施例所用的镍粉为上海杳田新材料科技有限公司提供的,铬粉为上海杳田新材料科技有限公司提供的,三氧化二铬粉为上海杳田新材料科技有限公司提供的,氮化硼纳米片为南京先丰纳米材料科技有限公司提供的。
比较例1
用电子天平分别称取60wt%镍粉、15wt%铬粉和25wt%三氧化二铬粉;
将镍粉、铬粉和三氧化二铬粉放入卧式行星球磨机中加入异丙醇进行球磨,球磨过程中球料比例为4:1,球磨机的转速为300r/min,球磨6小时,得到混合浆料;
将上述混合浆料放在真空干燥箱中80℃干燥,然后研磨成粉末,得到混合粉末;
将上述混合粉末进行喷雾造粒,得到球形等离子喷涂喂料;
将上述等离子喷涂喂料进行等离子喷涂,电流为800A,电压为40V,主气氩气流量35slm,辅气氦气流量35slm,等离子喷涂喷嘴距离喷涂基体距离80mm,得到镍基复合涂层。
实施例1
用电子天平分别称取60wt%镍粉、15wt%铬粉和25wt%三氧化二铬粉;
将镍粉、铬粉和三氧化二铬粉放入卧式行星球磨机中加入异丙醇进行球磨,球磨过程中球料比例为4:1,球磨机的转速为300r/min,球磨6小时,得到混合浆料;
将上述混合浆料放在真空干燥箱中80℃干燥,然后研磨成粉末,得到混合粉末;
将氮化硼纳米片放在异丙醇中进行超声分散4小时,得到氮化硼纳米片分散液;
将所述混合粉末放入氮化硼纳米片分散液中,用均质机进行搅拌分散,转速为5000rpm,时间为5小时,将得到的混合液在真空干燥箱中80℃干燥,然后研磨成粉末,得到粉体,氮化硼纳米片在粉体中的质量含量为0.5%;
将聚乙二醇溶解在水中,聚乙二醇在水中的质量分数为10wt%,得到聚乙二醇溶液;将上述粉体、水和聚乙二醇溶液按照质量分数比为45:45:10混合, 得到浆料;将得到的浆料进行喷雾造粒,喷嘴转速2100rpm,喷嘴进口温度270℃,出口温度115℃,得到球形等离子喷涂喂料;
将上述等离子喷涂喂料进行等离子喷涂,电流为800A,电压为40V,主气氩气流量35slm,辅气氦气流量35slm,等离子喷涂喷嘴距离喷涂基体距离90mm,得到氮化硼纳米片增强镍基复合涂层。
实施例2
用电子天平分别称取60wt%镍粉、15wt%铬粉和25wt%三氧化二铬粉;
将镍粉、铬粉和三氧化二铬粉放入卧式行星球磨机中加入异丙醇进行球磨,球磨过程中球料比例为4:1,球磨机的转速为300r/min,球磨6小时,得到混合浆料;
将上述混合浆料放在真空干燥箱中80℃干燥,然后研磨成粉末,得到混合粉末;
将氮化硼纳米片放在异丙醇中进行超声分散4小时,得到氮化硼纳米片分散液;
将所述混合粉末放入氮化硼纳米片分散液中,用均质机进行搅拌分散,转速为5000rpm,时间为5小时,将得到的混合液在真空干燥箱中80℃干燥,然后研磨成粉末,得到粉体,氮化硼纳米片在粉体中的质量含量为1%;
将聚乙二醇溶解在水中,聚乙二醇在水中的质量分数为10wt%,得到聚乙二醇溶液;将上述粉体、水和聚乙二醇溶液按照质量分数比为45:45:10混合,得到浆料;将得到的浆料进行喷雾造粒,喷嘴转速2100rpm,喷嘴进口温度270℃,出口温度115℃,得到球形等离子喷涂喂料;
将上述等离子喷涂喂料进行等离子喷涂,电流为800A,电压为40V,主气氩气流量35slm,辅气氦气流量35slm,等离子喷涂喷嘴距离喷涂基体距离90mm,得到氮化硼纳米片增强镍基复合涂层。
实施例3
用电子天平分别称取镍粉、铬粉和三氧化二铬粉;
将镍粉、铬粉和三氧化二铬粉放入卧式行星球磨机中加入异丙醇进行球磨,球磨过程中球料比例为4:1,球磨机的转速为300r/min,球磨6小时,得到混合浆料;
将上述混合浆料放在真空干燥箱中80℃干燥,然后研磨成粉末,得到混合粉末;
将氮化硼纳米片放在异丙醇中进行超声分散4小时,得到氮化硼纳米片分散液;
将所述混合粉末放入氮化硼纳米片分散液中,用均质机进行搅拌分散,转速为5000rpm,时间为5小时,将得到的混合液在真空干燥箱中80℃干燥,然后研磨成粉末,得到粉体,氮化硼纳米片在粉体中的质量含量为1.5%;
将聚乙二醇溶解在水中,聚乙二醇在水中的质量分数为10wt%,得到聚乙二醇溶液;将上述粉体、水和聚乙二醇溶液按照质量分数比为45:45:10混合,得到浆料;将得到的浆料进行喷雾造粒,喷嘴转速2100rpm,喷嘴进口温度270℃,出口温度115℃,得到球形等离子喷涂喂料;
将上述等离子喷涂喂料进行等离子喷涂,电流为800A,电压为40V,主气氩气流量35slm,辅气氦气流量35slm,等离子喷涂喷嘴距离喷涂基体距离90mm,得到氮化硼纳米片增强镍基复合涂层。
性能检测
对本发明实施例1制备得到的等离子喷涂喂料进行SEM检测,检测结果如图2所示,由图2(a)可知,粉末球形度良好,尺寸分布均匀;由图2(b)可知,少层氮化硼纳米片均匀分散在粉末中。
对实施例1中使用的原始BNNP以及制备得到的等离子喷涂喂料进行Raman(拉曼光谱)检测,检测结果如图3所示,由图3可知,对比原始BNNP,等离子喷涂喂料检测的G峰发生蓝移(右偏),且半峰宽变大,这说明原始氮化硼纳米片经过分散和喷雾造粒处理后可以减薄并均匀分散在粉末内。
对本发明实施例和比较例制备的镍基复合涂层进行XRD检测,检测结果如图4所示,由图4可知,镍基复合涂层中主要有γ-NiCr、Cr
2O
3和少量NiO。
对本发明实施例1制备的复合涂层断面进行SEM检测,检测结果如图5所示,由图5可知,少层氮化硼纳米片均匀分散在涂层内部。
对本发明实施例和比较例制备的镍基复合涂层进行硬度检测,经过显微硬度计(XD-1000TMC/LCD,上海泰明光学仪器有限公司)测量得到涂层不添加氮化硼纳米片和添加氮化硼纳米片含量分别为0.5wt.%、1.0wt.%、1.5wt.% 的硬度分别是548HV
0.2,609HV
0.2,620HV
0.2及575HV
0.2,如图6所示,可知,添加1.5wt.%氮化硼纳米片的氮化硼纳米片增强镍基复合涂层硬度略有下降,可能主要原因是氮化硼纳米片不可避免的会发生团聚,会导致涂层内形成孔洞,影响其致密性,造成硬度的下降。
对本发明实施例1~3和比较例1制备的复合涂层进行摩擦磨损测试,经过摩擦磨损试验机(HT1000,兰州中科凯华科技开发有限公司)在载荷20N、转速300rpm和1200rpm、旋转半径2mm和对磨球为直径为4mm的氧化铝球测量得到涂层的摩擦系数和磨损量如图7(转速300rpm)、图8(转速1200rpm)和图9所示,可知,随着氮化硼纳米片的增多,涂层的耐磨和减摩性能提升。
本发明提供了一种新的氮化硼纳米片增强镍基复合涂层材料体系,即氮化硼纳米片(Boron Nitride Nanoplatelet,BNNP)增强的(NiCr/Cr
2O
3,NCCO)镍基高温复合涂层,并以镍粉,铬粉,三氧化二铬粉,氮化硼纳米片为原始粉末,采用均质机,喷雾造粒制备等离子喷涂喂料,以及等离子喷涂技术制备复合涂层,提高复合涂层的力学性能,发展兼备优异的高温摩擦学性能和良好高温抗氧化性能的BNNP/NCCO复合涂层材料体系。本发明提供了一种兼具轻质、高强韧性和润滑性能的氮化硼纳米片增强NiCr/Cr
2O
3复合涂层的制备方法,即采用均质机分散结合喷雾造粒技术制备喷涂喂料,然后将得到的粉末利用等离子喷涂技术烧结制备复合涂层,获得兼备高强度、耐磨损、低摩擦系数等多种优异性能配合的新型复合涂层。本发明选择具有较优异的抗氧化性能、耐腐蚀性能且与镍基高温合金以及涂层材料均有良好相容性的NiCr为基体相,以Cr
2O
3作为增强相提升涂层的耐磨性能,以BNNP作为自润滑相,采用等离子喷涂技术制备出具有耐高温、耐磨损、耐腐蚀、低摩擦系数等多种优异性能配合的新型复合涂层。
以上所述的仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
- 一种氮化硼纳米片增强镍基复合涂层的制备方法,包括:将镍粉、铬粉和三氧化二铬粉混合,得到混合粉末;将所述混合粉末和氮化硼纳米片分散液混合后干燥,得到粉体;将所述粉体进行喷雾造粒,得到喷涂喂料;将所述喷涂喂料进行等离子喷涂,得到氮化硼纳米片增强镍基复合涂层。
- 根据权利要求1所述的方法,其特征在于,所述混合粉末的制备方法包括:将镍粉、铬粉和三氧化二铬粉用异丙醇进行球磨,得到浆料;将所述浆料进行干燥后研磨,得到混合粉末;所述球磨过程中的球料比例为(3~5):1,转速为200~400r/min,球磨时间为5~7小时;所述干燥的温度为70~90℃。
- 根据权利要求1所述的方法,其特征在于,所述镍粉、铬粉和三氧化二铬粉的质量比为(55~65):(10~20):(20~30)。
- 根据权利要求1所述的方法,其特征在于,所述氮化硼纳米片分散液的制备方法包括:将氮化硼纳米片和异丙醇混合进行超声分散,得到氮化硼纳米片分散液;所述超声分散的时间为3~5小时。
- 根据权利要求1所述的方法,其特征在于,所述混合粉末和氮化硼纳米片分散液混合的方法包括:将混合粉末放入氮化硼纳米片分散液中进行搅拌分散;所述搅拌分散过程中的转速为4500~5500rpm,所述搅拌分散的时间为4~6小时。
- 根据权利要求1所述的方法,其特征在于,所述混合粉末和氮化硼纳米片分散液混合后干燥的温度为70~90℃。
- 根据权利要求1所述的方法,其特征在于,所述氮化硼纳米片在粉体中的质量含量为0.5~1.5%。
- 根据权利要求1所述的方法,其特征在于,所述等离子喷涂过程中的电流为750~850A,电压为35~45V,主气氩气流量为30~40slm,辅气氦气流量为30~40slm。
- 根据权利要求1所述的方法,其特征在于,所述等离子喷涂过程中喷嘴距离喷涂基体的距离为70~90mm。
- 一种权利要求1所述的方法制备得到的氮化硼纳米片增强镍基复合涂层。
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CN117884634B (zh) * | 2024-03-18 | 2024-05-31 | 天津大学 | 氮化硼增强铜基复合材料及其制备方法 |
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