CN114959689A - Particle reinforced alloy composite powder for ultra-high-speed laser cladding - Google Patents
Particle reinforced alloy composite powder for ultra-high-speed laser cladding Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 89
- 239000002245 particle Substances 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 238000004372 laser cladding Methods 0.000 title claims abstract description 42
- 239000002028 Biomass Substances 0.000 claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000011159 matrix material Substances 0.000 claims abstract description 28
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- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims description 41
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000003610 charcoal Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000005253 cladding Methods 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
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- 238000007254 oxidation reaction Methods 0.000 description 8
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
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- 210000000988 bone and bone Anatomy 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the field of metal materials, and particularly relates to particle reinforced alloy composite powder for ultrahigh-speed laser cladding. In order to solve the problems, the invention prepares particle reinforced alloy composite powder for ultra-high-speed laser cladding, provides alloy composite powder and biomass carbon particles, improves the fluidity of metal powder by nitriding the biomass carbon particles, and enhances the bonding effect between the composite powder and a matrix material by forming coordinate bonds between the biomass carbon particles and the matrix material.
Description
Technical Field
The invention belongs to the field of metal materials, and particularly relates to particle reinforced alloy composite powder for ultrahigh-speed laser cladding.
Background
In recent decades, industries such as engineering machinery, coal mine machinery, ferrous metallurgy, petrochemical industry, automobiles, ships and the like in China develop rapidly, a large amount of mechanical equipment is put into production and use, various damages inevitably occur to parts of the equipment in the service process, and a large amount of economic losses and environmental hazards are caused because the parts are scrapped and failed due to surface abrasion, cracks and the like. The laser cladding technology is an advanced laser processing technology, and forms a cladding layer which is metallurgically combined with a workpiece on the surface of the workpiece by utilizing materials with better physical and chemical properties in a laser beam heating and melting mode on the basis of the existing workpiece, thereby achieving the purposes of improving the surface property of the workpiece and repairing the damaged surface of the workpiece. The laser cladding technology is one of material surface modification technologies, and the surface of a workpiece can obtain good properties such as strength, hardness, wear resistance, corrosion resistance and the like by selecting a proper cladding material and a proper processing technology.
The Chinese patent with the application number of 201910257153.7 discloses an ultrahigh-hardness laser cladding composite coating material and a preparation method thereof, wherein the coating consists of five elements of Ni, Mo, Si, Nb and C, the Ni, the Mo and the Si exist in an equimolar ratio and have the sum of mass percent of 85-95%, and the balance is a compound NbC; the granularity of the single element powder is 100-300 meshes, the coating thickness is 0.8-2mm, and the main phase is Mo 2 Ni 3 Si and Ni 3 Mo 3 C, the average hardness is 1200-1800 HV; firstly, ball milling and mixing the unit element powder, adjusting the powder to be viscous, presetting the powder on the surface of a matrix for drying, and then carrying out laser cladding to obtain the nickel-based composite coating. The obtained cladding layer has fine and uniform tissue, no obvious air holes and cracks, is completely metallurgically bonded with the base material, and can realize the surface modification and repair of parts by preparing the coating on the surface of the mechanical part.
The Chinese patent with the application number of 201811506663.5 discloses a preparation method of an ultrahigh-strength and toughness forming layer, wherein the intermediate transition alloy of low phosphorus and sulfur, namely iron carbon, iron chromium, iron silicon, iron manganese, iron aluminum, iron vanadium and pure nickel, C, is selected according to the following element mass percentages: 0.25-0.28%, Cr: 13.15-14%, Ni: 0.8-2%, Si: 0.92 to 1.2%, Mn: 0.9-1.02%, Al: 0.5-0.6%, V: 0.13-0.21% of Fe and the balance of Fe, wherein the sum of the mass percentages is 100%, and the Fe are prepared into an alloy mixture; vacuum melting, and atomizing nitrogen with the purity of 99.999 percent to obtain the iron-based alloy powder for the ultrahigh-strength and toughness double-phase laser forming. Determining a laser scanning track, adjusting the distance, cladding alloy powder on the surface of a base material, keeping the temperature of 200-300 ℃ for 2 hours, and then air-cooling to obtain the ultrahigh-strength and high-toughness laser forming layer.
In the prior art, when the powder component is used for laser cladding, poor molten pool fluidity is promoted to generate pores, so that the problems of cracking and pores of a laser cladding layer are the biggest obstacles for industrialization.
Disclosure of Invention
In order to solve the problems, the invention prepares particle reinforced alloy composite powder for ultrahigh-speed laser cladding, provides alloy composite powder and biomass carbon particles, improves the fluidity of metal powder by adding aminated biomass carbon particles, and enhances the binding action between the composite powder and a matrix material by forming coordinate bonds between the biomass carbon particles and the matrix material.
The technical scheme for solving the problems is as follows:
a particle reinforced alloy composite powder for ultra-high-speed laser cladding is composed of alloy composite powder and biomass carbon particles, and the mixture ratio of the alloy composite powder to the biomass carbon particles is as follows: 80-98% of cobalt matrix metal powder and 2-20% of biomass charcoal particles, wherein the cobalt matrix metal powder comprises the following chemical components in percentage by mass: 5.0-15.0% of Cr, 0.5-10.0% of W, 1.0-10.0% of Mo, 0.5-2.0% of Si, 2.0-5.0% of Fe, 0.5-2.0% of V, less than or equal to 3.0% of Ni, less than or equal to 1.0% of Mn, less than or equal to 0.10% of B, and the balance of Co and inevitable impurities;
the biomass charcoal particles are prepared by carbonizing biomass and then doping nitrogen.
Further, the preparation method of the biomass charcoal particles comprises the following steps: and (2) putting the cleaned and dried biomass material into a tubular furnace, heating and carbonizing the biomass material in an inert atmosphere, mixing the biomass material with mixed strong acid after ball milling, performing suction filtration, centrifugation, washing and vacuum drying after ultrasonic treatment reaction, and performing ammonia gas treatment at high temperature to obtain the nitrogen-doped biomass carbon particles.
The invention has the following beneficial effects:
according to the invention, a biomass charcoal structure is introduced into the composite powder, the toughness of the biomass charcoal is utilized to enhance the wear resistance and corrosion resistance of the surface after cladding processing, and meanwhile, the good fluidity of the biomass charcoal is utilized to improve the fluidity of the metal powder; by further carrying out nitrogen doping treatment on the biomass carbon, when the metal alloy is fused with the surface of the matrix material in a molten state, lone-pair electrons provided by nitrogen elements form coordination bonds with partial metal elements in the matrix material, so that the binding effect between the composite powder and the aggregate material is enhanced.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The biomass material used in the invention is sturgeon fish scales.
Example 1
The mixture ratio of the alloy composite powder to the biomass carbon particles is as follows: 95% of cobalt matrix metal powder and 5% of biomass charcoal particles, wherein the cobalt matrix metal powder comprises the following chemical components in percentage by mass: 5.0% Cr, 10.0% W, 1.0% Mo, 2.0% Si, 2.0% Fe, 0.5% V, the balance Co and unavoidable impurities.
The biomass charcoal particles are prepared by carbonizing biomass and then doping nitrogen, and the preparation method comprises the following steps: taking a cleaned and dried biomass material, placing the biomass material between corundum plates, transferring the biomass material into a tubular furnace, and heating and carbonizing the biomass material under the nitrogen atmosphere, wherein the heating condition of the tubular furnace is as follows: the heating rate is 1 ℃/min, the temperature is increased from room temperature to 200 ℃, the temperature is maintained for 2h, the heating rate is 2 ℃/min, the temperature is increased to 400 ℃, the temperature is maintained for 1h, a carbonized biomass material is obtained, the obtained carbonized biomass material is subjected to ball milling under the conditions of 300r/min and 3h, and the ball-milled biomass material is mixed with mixed strong acid according to the volume ratio: 98% concentrated H 2 SO 4 : 68% concentrated HNO 3 Heating to 55 ℃, ultrasonically dispersing for 2 hours under the conditions of 400w and 20kHz pulse ultrasonic waves, heating to 110 ℃ for reacting for 1 hour, diluting acid liquor by using distilled water after the reaction is finished, performing suction filtration after the ultrasonic treatment reaction, repeatedly performing suction filtration by using a 1-micron microfiltration membrane and an acid-base funnel during the suction filtration until carbide in filtrate can not be filtered out, centrifuging by using a high-speed centrifuge, recovering again, repeatedly washing and collecting the carbide after acid oxidation by using distilled water until the filtrate is neutral, performing vacuum drying on the recovered carbide for 2 hours at 110 ℃ to obtain dried carbide after acid oxidation, introducing ammonia gas into the obtained carbide after acid oxidation at high temperature, specifically placing the carbide after acid oxidation in a tubular furnace, firstly introducing nitrogen gas to discharge air in the tube, introducing ammonia gas after the air in the tube is completely discharged, and reacting to obtain the nitrogen-doped biomass carbon particles.
The preparation method of the composite powder comprises the following steps: preparing the raw materials according to the alloying proportion of the raw material components; ball-milling the raw materials, placing the ball-milled raw materials in a vacuum melting chamber, and heating the ball-milled raw materials to be molten by medium-frequency induction, wherein the ball-milling conditions are as follows: 200r/min, ball milling for 2h, and the vacuum degree of a smelting chamber is 10 -1 Pa, adopting a gas atomization method to prepare powder, spraying gas with argon pressure of 1.2MPa, collecting the powder, carrying out particle size screening, screening metal powder with particle size range of 10-100 mu m, and simultaneously screening biomass charcoal particles with particle size range of 10-100 mu m; and uniformly mixing the screened metal powder and the biomass charcoal particles in a mixer according to the corresponding proportion to obtain the biomass charcoal composite material.
The application of the particle reinforced alloy composite powder for ultra-high-speed laser cladding in laser cladding manufacture is characterized in that the prepared composite powder is subjected to surface manufacture and repair by adopting an ultra-high-speed laser cladding technology and matching with different processes.
The specific process comprises the following steps:
and machining the surface of the part to be machined.
And wiping the surface of the part to be processed by using acetone to remove surface grease.
And planning a laser cladding path according to the surface geometry of the part, and formulating process parameters.
Carrying out cladding processing on the surface of a part to be processed by adopting an ultrahigh-speed laser cladding system, and adopting the following process parameters: the laser power is 1kw, the diameter of a light spot is 1mm, the powder feeding speed is 5kg/h, the laser scanning speed is 20m/min, the lap joint rate is 30%, the single-layer cladding thickness is 25 mu m, the laser cladding head has the argon protection function, and the argon flow is 15L/min.
Example 2
Compared with the embodiment 1, the proportion of the alloy composite powder and the biomass charcoal particles and the chemical components and the mass percentage of the cobalt matrix metal powder are different, and specifically the following components are adopted: 98% of cobalt base metal powder and 2% of biomass carbon particles, wherein the cobalt base metal powder comprises the following chemical components in percentage by mass: 15.0% of Cr, 0.5% of W, 10.0% of Mo, 0.5% of Si, 5.0% of Fe, 2.0% of V, and the balance of Co and inevitable impurities;
the tubular furnace heating condition, the ball milling condition and the mixture ratio of the mixed strong acid are different in the biomass carbon particle preparation process, and the method specifically comprises the following steps: the heating conditions of the tube furnace were: the heating rate is 3 ℃/min, the temperature is increased from room temperature to 300 ℃, the temperature is maintained for 4h, the heating rate is 5 ℃/min, the temperature is increased to 500 ℃, and the temperature is maintained for 3 h; the ball milling conditions are as follows: 500r/min, and ball milling for 4 h; the mixed strong acid comprises the following components in percentage by volume: 98% concentrated H 2 SO 4 : 68% concentrated HNO 3 ＝1:3。
The preparation method of the composite powder has different parameters, and specifically comprises the following steps: vacuum degree of the smelting chamber is 10 -2 Pa, and the pressure of the spraying gas argon gas is 3.7 MPa.
The method comprises the following steps of performing cladding processing on the surface of a part to be processed by adopting an ultrahigh-speed laser cladding system, wherein the processing parameters are different, and specifically comprise the following steps: the laser power is 2kw, the diameter of a light spot is 1mm, the powder feeding speed is 8kg/h, the laser scanning speed is 50m/min, the lap joint rate is 40%, the single-layer cladding thickness is 50 mu m, the laser cladding head has the argon protection function, and the argon flow is 30L/min.
The rest of the parameters, conditions and preparation were as in example 1.
Example 3
Compared with the embodiment 1, the proportion of the alloy composite powder and the biomass charcoal particles and the chemical components and the mass percentage of the cobalt matrix metal powder are different, and specifically the following components are adopted: 97 percent of cobalt matrix metal powder and 3 percent of biomass charcoal particles, wherein the cobalt matrix metal powder comprises the following chemical components in percentage by mass: 10.0% Cr, 8.0% W, 6.0% Mo, 1.5% Si, 3.0% Fe, 1.5% V, the balance Co and unavoidable impurities;
the tubular furnace heating condition, the ball milling condition and the mixture ratio of the mixed strong acid are different in the biomass carbon particle preparation process, and the method specifically comprises the following steps: the heating conditions of the tube furnace were: the heating rate is 2 ℃/min, the temperature is increased from room temperature to 300 ℃, the temperature is maintained for 3h, the heating rate is 3 ℃/min, the temperature is increased to 400 ℃, and the temperature is maintained for 2 h; the ball milling conditions are as follows: ball milling for 3h at the speed of 400 r/min; the mixed strong acid comprises the following components in percentage by volume: 98% concentrated H 2 SO 4 : 68% concentrated HNO 3 ＝1:2。
The preparation method of the composite powder has different parameters in part, and specifically comprises the following steps: vacuum degree of the smelting chamber is 10 -2 Pa, and the pressure of the spraying gas argon is 3.0 MPa.
The method comprises the following steps of carrying out cladding processing on the surface of a part to be processed by adopting an ultrahigh-speed laser cladding system, wherein the method adopts different process parameters, and specifically comprises the following steps: the laser power is 2kw, the diameter of a light spot is 1mm, the powder feeding speed is 6kg/h, the laser scanning speed is 30m/min, the lap joint rate is 30%, the single-layer cladding thickness is 30 mu m, the laser cladding head has the argon protection function, and the argon flow is 20L/min.
The rest of the parameters, conditions and preparation were as in example 1.
Comparative example 1
Compared with the embodiment 3, the biomass carbon particles are replaced by the nitrogen-containing carbon particles, and the alloy composite powder and the nitrogen-containing carbon particles are proportioned as follows: 97% cobalt matrix metal powder and 3% nitrogen containing carbon particles.
The preparation method of the nitrogen-containing carbon particles comprises the following steps: putting the dried carbon particles into a tube furnace, and heating the carbon particles in a nitrogen atmosphere under the following heating conditions: the heating rate is 2 ℃/min, the temperature is increased from room temperature to 300 ℃, the temperature is maintained for 3h, the heating rate is 3 ℃/min, the temperature is increased to 400 ℃, and the temperature is maintained for 2 h; after heating, putting the mixture into a ball milling tank for ball milling, wherein the ball milling conditions are as follows: ball milling for 3h at a speed of 400 r/min; mixing the carbon particles obtained after ball milling with mixed strong acid, wherein the mixed strong acid comprises the following components in percentage by volume: 98% thickH 2 SO 4 : 68% concentrated HNO 3 Heating to 55 ℃, ultrasonically dispersing for 2 hours under the condition of pulse ultrasonic waves of 400w and 20kHz, heating to 110 ℃ for reacting for 1 hour, diluting the acid liquor by using distilled water after the reaction is finished, performing suction filtration after the ultrasonic treatment reaction, repeatedly performing suction filtration by using a 1-micron microfiltration membrane and an acid-base-resistant funnel during the suction filtration until carbon particles in filtrate can not be filtered out, centrifuging by using a high-speed centrifuge, recovering again, repeatedly washing and collecting the carbon particles after acid oxidation by using distilled water until the filtrate is neutral, performing vacuum drying on the recovered carbon particles for 2 hours at 110 ℃ to obtain dried carbon particles after acid oxidation, introducing ammonia gas into the obtained carbon particles after acid oxidation at high temperature, specifically placing the carbon particles after acid oxidation in a tubular furnace, introducing nitrogen gas to discharge air in the tube, introducing ammonia gas after the air in the tube is discharged completely, obtaining the nitrogen-containing carbon particles after reaction.
The rest of the parameters, conditions and preparation were as in example 3.
Comparative example 2
Compared with the embodiment 3, the biomass carbon particles are replaced by the carbon particles, and the alloy composite powder and the carbon particles are proportioned as follows: 97% cobalt matrix metal powder and 3% carbon particles.
The treatment method of the carbon particles comprises the following steps: putting the dried carbon particles into a tubular furnace, and heating under the nitrogen atmosphere, wherein the heating condition is as follows: the heating rate is 2 ℃/min, the temperature is increased from room temperature to 300 ℃, the temperature is maintained for 3h, the heating rate is 3 ℃/min, the temperature is increased to 400 ℃, and the temperature is maintained for 2 h; after heating, putting the mixture into a ball milling tank for ball milling, wherein the ball milling conditions are as follows: 400r/min and ball milling for 3 h.
The rest of the parameters, conditions and preparation were as in example 3.
Comparative example 3
Compared with example 3, no nitrogen doping is performed on the biomass charcoal particles.
The preparation method of the biomass charcoal particles comprises the following steps:
taking a cleaned and dried biomass material, placing the biomass material between corundum plates, transferring the biomass material into a tubular furnace, and heating and carbonizing the biomass material under the nitrogen atmosphere, wherein the heating condition of the tubular furnace is as follows: the heating rate is 2 ℃/min, the temperature is increased to 300 ℃ from the room temperature, the temperature is maintained for 3h, the heating rate is 3 ℃/min, the temperature is increased to 400 ℃, the temperature is maintained for 2h, a carbonized biomass material is obtained, and the obtained carbonized biomass material is subjected to ball milling for 3h, wherein the ball milling condition is 400 r/min.
The rest of the parameters, conditions and preparation were as in example 3.
Comparative example 4
Compared with example 3, the biomass material used is different, in this comparative example, shell is selected as the biomass material, and the specific parameter conditions and preparation process refer to example 3.
And (4) relevant testing:
the composite powders prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to the relevant tests, and the test performance parameters thereof are shown in Table 1.
TABLE 1
| Group of | Particle size μm | Fluidity s/50g | Sphericity% | D 50 /μm |
| Example 1 | 10-100 | 45 | 90 | 45 |
| Example 2 | 10-100 | 40 | 91 | 42 |
| Example 3 | 10-100 | 35 | 93 | 35 |
| Comparative example 1 | 10-100 | 50 | 86 | 50 |
| Comparative example 2 | 10-100 | 56 | 85 | 55 |
| Comparative example 3 | 10-100 | 52 | 82 | 52 |
| Comparative example 4 | 10-100 | 48 | 88 | 48 |
The surface properties of the composite powders prepared in examples 1 to 3 and comparative examples 1 to 4 after being subjected to the ultra-high-rate laser cladding processing were tested, and the results are shown in table 2.
TABLE 2
It can be seen from the above test results that the relevant performance of examples 1 to 3 is better than that of comparative examples 1 to 4, and from the comparison between the test results of comparative example 3 and example 3, the corrosion resistance and the service life of the biomass carbon material are both effectively improved after nitrogen doping, which indicates that coordination bonds are formed between lone-pair electrons on the N element contained in the composite powder prepared after nitrogen doping and the metal element contained in the matrix material in a molten state, and the bonding effect between the composite powder and the matrix material is effectively improved. Compared with the test results of the comparative example 1, the comparative example 4 and the example 3, the performance of the biomass material is reduced after the biomass material is replaced by the nitrogen-containing carbon particles and another biomass material, which shows that the biomass material used by the invention can have better fusion with the matrix metal powder after being treated, and simultaneously, the specific carbon skeleton structure of the biomass material used by the invention can effectively improve the surface performance of the composite powder after being subjected to ultrahigh-speed laser cladding processing.
The Co-based alloy powder has good high-temperature performance, corrosion resistance and wear resistance, and the Co-based alloy has good wettability. The melting point of the alloy is lower than that of carbide, Co element is in a molten state firstly after the alloy is heated, and the Co element and other elements form a new phase firstly when the alloy is solidified, so that the alloy is very beneficial to strengthening a cladding layer. Because the carbon material has good lubricity and chemical stability, in order to improve the uniformity and the fusibility of an alloy structure in the laser cladding process, the biomass carbon particles are introduced. Due to the special components and the structure contained in the biomass material, the biomass material can form a biomass charcoal material with special properties after carbonization. According to the invention, the fish scales are used as biomass materials, the fish scales are composed of an inner layer and an outer layer, the outer layer is a mineralized bone layer, the inner layer is a flexible collagen layer, the collagen layer is composed of collagen fibers, the fibers are arranged in an orthogonal or double-twisted splint-shaped distribution, the collagen fibers of each layer are arranged in a directional parallel manner, a certain included angle is formed between the layers, and the hydroxyapatite granular layer contained in the fish scales has better toughness and strength.
In order to further improve the combination between the added biomass particles and the matrix metal, the invention carries out further nitrogen doping on the basis of obtaining the carbonized biomass material to obtain the nitrogen-doped biomass charcoal particles. The nitrogen element contains lone-pair electrons, the matrix material contains metal elements, and coordination bonds are formed between vacant orbits provided by the metal elements in the matrix material and the lone-pair electrons contained in the nitrogen element contained in the composite powder in a molten state, so that the binding force between the composite powder and the matrix material is further enhanced. When the ultrahigh-speed laser cladding is carried out, the prepared composite powder can form a solid solution with a matrix material, and part of the prepared composite powder can be directly precipitated as a second phase, the second phase is uniformly distributed in the matrix phase in the form of fine and dispersed particles, so that a remarkable strengthening effect can be generated, and meanwhile, as a plurality of metal elements also exist in the added alloy composite powder, coordination bonds can be formed between nitrogen-doped biomass carbon particles contained in the alloy composite powder and the metal elements contained in the alloy composite powder, so that the binding force between the biomass carbon particles and the metal elements in the alloy composite powder is increased; the prepared biomass carbon particles have a twisted layered carbon structure, so that the deformation resistance of the prepared alloy is further improved, and the wear resistance, corrosion resistance and deformation resistance of the cladding processing surface are further improved.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The particle reinforced alloy composite powder for ultra-high-speed laser cladding is characterized by comprising alloy composite powder and biomass carbon particles, and the mixture ratio of the alloy composite powder to the biomass carbon particles is as follows: 95-98% of cobalt matrix metal powder and 2-5% of biomass charcoal particles, wherein the cobalt matrix metal powder comprises the following chemical components in percentage by mass: 5.0-15.0% of Cr, 0.5-10.0% of W, 1.0-10.0% of Mo, 0.5-2.0% of Si, 2.0-5.0% of Fe, 0.5-2.0% of V, less than or equal to 3.0% of Ni, less than or equal to 1.0% of Mn, less than or equal to 0.10% of B, and the balance of Co and inevitable impurities;
the biomass charcoal particles are prepared by carbonizing biomass and then doping nitrogen.
2. The particle-reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 1, wherein the powder has sphericity of 90% or more, fluidity of 35-45s/100g, and D50 of 35-50 μm.
3. The particle reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 1, wherein the preparation method of the biomass charcoal particles comprises: and (2) taking the cleaned and dried biomass material, transferring the biomass material into a tubular furnace, heating and carbonizing the biomass material in an inert atmosphere, mixing the biomass material with mixed strong acid after ball milling, performing suction filtration, centrifugation, washing and vacuum drying after ultrasonic treatment reaction, and introducing ammonia gas at high temperature to obtain the nitrogen-doped biomass carbon particles.
4. The particle-reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 3, wherein the biomass material after washing and drying is placed between corundum plates and then put into a tube furnace for carbonization, and the heating conditions of the tube furnace are as follows: the heating rate is 1-3 ℃/min, the temperature is increased from the room temperature to 200 ℃ and 300 ℃, the temperature is maintained for 2-4h, the heating rate is 2-5 ℃/min, the temperature is increased to 400 ℃ and 500 ℃, and the temperature is maintained for 1-3 h.
5. The particle-reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 3, wherein the ball milling conditions are as follows: 300 and 500r/min, and ball milling for 3-4 h.
6. The particle-reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 3, wherein the strong acid is: concentrated H 2 SO 4 : concentrated HNO 3 ＝1:1-3，v/v。
7. The method for preparing the particle reinforced alloy composite powder for ultra high speed laser cladding according to any one of claims 1 to 6, comprising the steps of: preparing raw materials according to the alloying proportion of the raw material components; ball-milling the raw materials, placing the raw materials in a vacuum melting chamber, heating the raw materials to be molten by medium-frequency induction, preparing powder by adopting a gas atomization method, and screening metal powder with the particle size range of 10-100 mu m; screening biomass charcoal particles with the particle size range of 10-100 mu m; and uniformly mixing the screened metal powder and the biomass charcoal particles in a mixer according to the corresponding proportion to obtain the biomass charcoal composite material.
8. The method for preparing particle reinforced alloy composite powder for ultra-high speed laser cladding as claimed in claim 7, wherein vacuum degree of the vacuum melting chamber is 10 -1 -10 -2 Pa。
9. The use of the particle reinforced alloy composite powder for ultra-high speed laser cladding in laser cladding manufacture according to any one of claims 1 to 6, wherein the prepared composite powder is subjected to surface manufacture and repair by using an ultra-high speed laser cladding technology.
10. The application of the particle reinforced alloy composite powder for ultra-high speed laser cladding in laser cladding manufacturing according to claim 9, wherein an ultra-high speed laser cladding system is adopted to clad the surface of a part to be processed, and the following process parameters are adopted: the laser power is 1-2kw, the spot diameter is 1mm, the powder feeding speed is 5-8kg/h, the laser scanning speed is 20m-50m/min, the lap joint rate is 30% -40%, the single-layer cladding thickness is 25-50 μm, the laser cladding head has the argon protection function, and the argon flow is 15-30L/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951094A (en) * | 2016-05-26 | 2016-09-21 | 上海交通大学 | Method for preparing carbon nanotube reinforced coating layer by laser cladding |
| US20180016683A1 (en) * | 2015-01-05 | 2018-01-18 | Ibiden Co., Ltd. | Metal member with coat layer |
| CN108130530A (en) * | 2017-12-22 | 2018-06-08 | 北京机科国创轻量化科学研究院有限公司 | A kind of particle for ultrahigh speed laser melting coating enhances powder metal composition |
| CN108265288A (en) * | 2017-12-22 | 2018-07-10 | 北京机科国创轻量化科学研究院有限公司 | A kind of Co-based alloy powder for superelevation rate laser melting coating |
| CN112877686A (en) * | 2021-01-11 | 2021-06-01 | 西安理工大学 | Graphene/nickel-based composite powder for ultrahigh-speed laser cladding and preparation method thereof |
| US20210207251A1 (en) * | 2020-01-02 | 2021-07-08 | Beijing National Innovation Institute Of Lightweight Ltd | Iron-based metal powder for ultra-high-speed laser cladding, its preparation method and its application |
-
2022
- 2022-06-08 CN CN202210642958.5A patent/CN114959689B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180016683A1 (en) * | 2015-01-05 | 2018-01-18 | Ibiden Co., Ltd. | Metal member with coat layer |
| CN105951094A (en) * | 2016-05-26 | 2016-09-21 | 上海交通大学 | Method for preparing carbon nanotube reinforced coating layer by laser cladding |
| CN108130530A (en) * | 2017-12-22 | 2018-06-08 | 北京机科国创轻量化科学研究院有限公司 | A kind of particle for ultrahigh speed laser melting coating enhances powder metal composition |
| CN108265288A (en) * | 2017-12-22 | 2018-07-10 | 北京机科国创轻量化科学研究院有限公司 | A kind of Co-based alloy powder for superelevation rate laser melting coating |
| US20210207251A1 (en) * | 2020-01-02 | 2021-07-08 | Beijing National Innovation Institute Of Lightweight Ltd | Iron-based metal powder for ultra-high-speed laser cladding, its preparation method and its application |
| CN112877686A (en) * | 2021-01-11 | 2021-06-01 | 西安理工大学 | Graphene/nickel-based composite powder for ultrahigh-speed laser cladding and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 唐洋洋;袁守谦;杨潘;杨柳;冯璐;: "激光熔覆对钛合金性能的影响", 特种铸造及有色合金, no. 11 * |
| 岳学庆;段文艳;薛云;: "石墨包裹Ni纳米颗粒的制备及其摩擦磨损性能", 非金属矿, no. 04 * |
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