CN105401042B - Application of the high-entropy alloy powder in laser melting coating - Google Patents
Application of the high-entropy alloy powder in laser melting coating Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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
- 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
- C23C24/106—Coating with metal alloys or metal elements only
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Abstract
The invention discloses application of the high-entropy alloy powder in laser melting coating, high-entropy alloy powder is made up of Fe, Ni, Cr, Al, Cu and Mn element powders, and composition is expressed as FeNiCrAlCuMnx, the mol ratio that x is Mn and its span is 0~1.Proportioning calculating is carried out according to the mol ratio of respective element, it is sufficiently mixed after the quality of each component of precise with uniform, after high-entropy alloy powder and ethanol are mixed, substrate material surface is coated uniformly on, cladding layer can be obtained by laser melting coating after drying.High-entropy alloy powder obtains the good cladding layer of shaping in laser melting coating, by material surface modifying and improves material hardness and wearability.
Description
The present patent application is the divisional application of parent application " high-entropy alloy powder and cladding layer preparation method and application ", female
The Application No. 201310471107X of case application, the applying date of parent application is on October 10th, 2013.
Technical field
The invention belongs to coating technology field, more particularly, it is related to a kind of high-entropy alloy powder material and cladding layer
Preparation method and application.
Background technology
High-entropy alloy is that the one kind proposed first by China Taiwan's scholars professor Ye Junwei middle nineteen nineties in last century is new
Type alloy, based on equimolar than there is the high-entropy alloy of the theory design of, the high entropy of mixing microstructure to simplify, nanometer is separated out
The tissue signatures such as thing, non crystalline structure, nanocrystal.Many pivot high-entropy alloys, break through based on traditional single element, many high entropys of pivot
Numerous metallic compound will not be not only formed after alloy graining, simple body-centered cubic or face-centered cubic phase is formed on the contrary
Or even noncrystalline, the gained number of phases is well below the number of phases that balance one after another is predicted.Therefore, designed by appropriate alloy formula,
The property combinations such as high rigidity, high processing hardening, high temperature resistant softening, high temperature oxidation resisting, corrosion-resistant, high resistivity can be obtained, therefore
With very big application potential.
So far, high-entropy alloy is mainly prepared using methods such as vacuum arc furnace melting and foundings, is also had using electrification
Learn deposition and the magnetron sputtering method for preparing high-entropy alloy film, but the film thickness prepared by these methods is only capable of reaching micron
Yardstick, it is difficult to play the advantage in terms of high-entropy alloy mechanical property, and there are certain requirements to base material.Laser melting coating is due to tool
There are high heating and cooldown rate, coating is metallurgical binding with matrix, and bond strength is high, and coating layer thickness reaches as high as several millimeters.
In addition, the rapid solidification feature of laser melting coating can refine alloy structure, so as to obtain higher hardness and anti-wear performance.Cause
This, is designed by appropriate alloy formula, and high-entropy alloy coating is obtained using laser melting coating, is made in steel matrix with low cost
Standby high-entropy alloy coating, has a very big significance for the practical application for expanding high-entropy alloy.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of laser being made up of completely metallic element
Cladding high-entropy alloy powder and cladding layer preparation method, carry out material surface modifying, improve material hardness and wearability.
The technical purpose of the present invention is achieved by following technical proposals：
High-entropy alloy powder, is made up of Fe, Ni, Cr, Al, Cu and Mn element powders, i.e. alloy powder composition is expressed as
Mol ratio that FeNiCrAlCuMnx, x are Mn and its span is 0~1, specifically, between described Fe, Ni, Cr, Al, Cu
For equimolar ratio, metal Mn consumption is adjusted, so that it is 0 using mole and Si (or remaining four kinds of element) mol ratio
~1, preferably 0.3-1, more preferred 0.5-0.7.
When being prepared, the mol ratio for being first according to respective element carries out proportioning calculating, each component of precise
It is sufficiently mixed after quality with uniform, the powder of various elements is weighed for example with electronic scale, is ground in mortar
Mill half an hour is well mixed it.Wherein from each component be purity be more than or equal to 99% powder, particle diameter be 100-
500 mesh, preferably 200-300 mesh.
It is applied to using the alloy powder of the present invention in laser melting coating welding, after high-entropy alloy powder and ethanol are mixed,
Substrate material surface is coated uniformly on, cladding layer can be obtained by laser melting coating after drying.Wherein described ethanol Analysis about Selection
Pure absolute ethyl alcohol, in high-entropy alloy powder and alcohol mixture, according to mass percent by 92~95% alloy powder
Ethanol with 5~8% is constituted.Upon mixing, pasty state or paste are formed, in order to continue to coat in substrate material surface, through applying
In substrate material surface formation preformed layer after covering, the preformed layer thickness is 1-2mm.
It is 42CrMo steel from matrix material when carrying out laser melting coating, technological parameter is：Laser power be 1550~
1650KW, spot diameter is 0.8~1.0mm, and sweep speed is 150~200mm/min, and defocusing amount is 0mm, and protective gas is used
Argon gas or helium, gas flow are 20~25L/min；It is preferred that laser power be 1580~1620KW, spot diameter be 0.8~
1.0mm, sweep speed is 180~200mm/min, and defocusing amount is 0mm, and protective gas uses argon gas, gas flow is 22~
25L/min。
Compared with prior art, the invention has the advantages that：
(1) in alloy powder of the present invention, the maximum performance that each element is given full play to outside basic element iron, Ni master are removed
It is used to improve material wetability and improves cladding layer capability, Cr mainly improves cladding layer hardness by solution strengthening and is used for
Cladding layer corrosion resistance is improved, Al mainly improves the high temperature oxidation resistance of cladding layer, and brilliant by solution strengthening effect and increase
Boundary's skid resistance improves cladding layer hardness.Further, since aluminium surface easily aoxidizes the oxide-film to form densification, add in the alloy
Plus Al can also improve the corrosion resistance of cladding layer, Cu is mainly used in improving cladding layer wearability, and Mn is mainly used in deoxidation.
(2) the invention provides a kind of high-entropy alloy powder being made up of completely metallic element, and obtained by laser melting coating
Obtained the good cladding layer of shaping.
(3) laser melting coating high-entropy alloy powder proposed by the present invention can be according to materials'use performance requirement, in larger model
The preparation of interior progress pivot alloy is enclosed, so as to change cladding layer capability.
Brief description of the drawings
Fig. 1 is FeNiCrAlCu cladding layer macro morphologies.
Fig. 2 is FeNiCrAlCuMn cladding layer macro morphologies.
Fig. 3 is FeNiCrAlCu cladding layer overall pictures.
Fig. 4 is FeNiCrAlCuMn cladding layer overall pictures.
Fig. 5 is FeNiCrAlCu cladding layer metallographic structures.
Fig. 6 is FeNiCrAlCuMn cladding layer metallographic structures.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.Each metallic element source is as shown in the table：
Matrix material select 42CrMo steel, using mechanical grinding remove oxide, go to degrease using acetone, its chemistry into
Divide as shown in following table (mass fraction %)
| C | Mn | Si | Cr | Mo | Ni | Cu |
| 0.38~0.45 | 0.50~0.80 | 0.17~0.37 | 0.90~1.20 | 0.15~0.25 | ≤0.030 | ≤0.030 |
Implemented by the following method：
1. carrying out FeNiCrAlCuMnx according to mol ratio, (wherein x is mol ratio, and its span is 0~1) high entropy conjunction
Golden powder mixture ratio is calculated, and the powder of various elements is weighed using electronic scale, and grinding half an hour is well mixed it in mortar.
2. 92~95% laser cladding powder and 5~8% ethanol are mixed into after pasty state or paste, matrix is coated in
Material surface, preformed layer thickness is 1-2mm, and cladding layer can be obtained by laser melting coating after air-drying.
3. select laser to use JK2003SM types Nd：YAG carries out laser melting coating.
4. metallographic structure facilities for observation uses OLYMPUS-GX51 metallographic microscopes, manufacturer：Japanese OLYMPUS (Olympics
Bath) company.
Case study on implementation 1
1. according to mol ratio FeNiCrAlCuMnx (taking x=0) high-entropy alloy powder proportioning is carried out to calculate：Fe is
20mol%, Ni are 20mol%, and Cr is 20mol%, and Al is 20mol%, and Cu is 20mol%, and various members are weighed using electronic scale
The powder of element.
2. pouring into mortar, grinding half an hour is well mixed it in mortar.
3. by the laser cladding powder prepared, 92% and 8% ethanol is mixed into after pasty state or paste, is coated in 42CrMo
Steel surface, coating thickness is 1mm, and laser melting coating is carried out after air-drying.
4. laser uses JK2003SM types Nd：YAG, laser cladding technological parameter is：Laser power is 1550KW, hot spot
A diameter of 0.8mm, sweep speed is 180mm/min, and defocusing amount is 0mm, and protective gas uses argon gas, and gas flow is 25L/
min。
5. being corroded after laser melting coating using chloroazotic acid, the metallograph of cladding layer is obtained.
The microhardness of cladding layer is measured using automatic turret digital display sclerometer, shown in experimental result following table, laser melts
Cover rear hardness and reached 490.8HV, significantly improved than mother metal.
Its wearability using MM-200 type determination of wear testing machine, specimen size is 7 × 7 × 25mm, and friction duty is
Dry grinding sliding friction, is loaded as 5kg, rotating speed is 200r/min, and experimental period is 1h；With quality (measurement before and after electronic scale measurement
It is preceding to be cleaned with ultrasonic washing instrument), the experimental results are shown inthe following table.As can be seen that the weightlessness of mother metal is 2.0 times of cladding layer,
Compared with mother metal, the wearability of cladding layer is significantly improved.
Case study on implementation 2
1. according to mol ratio FeNiCrAlCuMnx (taking x=1) high-entropy alloy powder proportioning is carried out to calculate：Fe is
16.67mol%, Ni are 16.67mol%, and Cr is 16.67mol%, and Al is 16.67mol%, and Cu is 16.66mol%, and Mn is
16.66mol%, total moles ratio is 100%, and use electronic scale weighs the powder of various elements.
2. pouring into mortar, grinding half an hour is well mixed it in mortar.
3. by the laser cladding powder prepared, 95% and 5% ethanol is mixed into after pasty state or paste, is coated in 42CrMo
Steel surface, coating thickness is 1mm, and laser melting coating is carried out after air-drying.
4. laser uses JK2003SM types Nd：YAG, laser cladding technological parameter is：Laser power is 1550KW, hot spot
A diameter of 0.8mm, sweep speed is 180mm/min, and defocusing amount is 0mm, and protective gas uses argon gas, and gas flow is 25L/
min。
5. being corroded after laser melting coating using chloroazotic acid, the metallograph of cladding layer is obtained.
The microhardness of cladding layer is measured using automatic turret digital display sclerometer, the experimental results are shown inthe following table, laser
Average hardness has reached 437.5HV after cladding, is significantly improved than mother metal.
Its wearability using MM-200 type determination of wear testing machine, specimen size is 7 × 7 × 25mm, and friction duty is
Dry grinding sliding friction, is loaded as 5kg, rotating speed is 200r/min, and experimental period is 1h；With quality (measurement before and after electronic scale measurement
It is preceding to be cleaned with ultrasonic washing instrument), the experimental results are shown inthe following table.As can be seen that the weightlessness of mother metal is 2.4 times of cladding layer,
Compared with mother metal, the wearability of cladding layer is significantly improved.
Case study on implementation 3
1. carrying out FeNiCrAlCuMnx (taking x=0.3) high-entropy alloy powder according to mol ratio matches each metallic element：
Fe, Ni, Cr, Al and Cu are equimolar, and Mn is the 0.3 of Cu molal quantitys, is well mixed and is used, with reference to above-mentioned case study on implementation
2. laser melting and coating process：Laser power is 1650KW, and spot diameter is 1.0mm, and sweep speed is 200mm/min,
Defocusing amount is 0mm, and protective gas uses helium, and gas flow is 20L/min
3. identical carry out performance test is used, it is as a result as shown in the table：
Hardness
Wearability
Case study on implementation 4
1. carrying out FeNiCrAlCuMnx (taking x=0.5) high-entropy alloy powder according to mol ratio matches each metallic element：
Fe, Ni, Cr, Al and Cu are equimolar, and Mn is the 0.5 of Cu molal quantitys, is well mixed and is used, with reference to above-mentioned case study on implementation
2. laser melting and coating process：Laser power is 1620KW, and spot diameter is 0.9mm, and sweep speed is 180mm/min,
Defocusing amount is 0mm, and protective gas uses helium, and gas flow is 22L/min
3. identical carry out performance test is used, it is as a result as shown in the table：
Hardness
Wearability
Case study on implementation 5
1. carrying out FeNiCrAlCuMnx (taking x=0.7) high-entropy alloy powder according to mol ratio matches each metallic element：
Fe, Ni, Cr, Al and Cu are equimolar, and Mn is the 0.7 of Cu molal quantitys, is well mixed and is used, with reference to above-mentioned case study on implementation
2. laser melting and coating process：Laser power is 1580KW, and spot diameter is 0.8mm, and sweep speed is 150mm/min,
Defocusing amount is 0mm, and protective gas uses helium, and gas flow is 20L/min
3. identical carry out performance test is used, it is as a result as shown in the table：
Hardness
Wearability
Exemplary description is done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (5)
1. application of the high-entropy alloy powder in laser melting coating, it is characterised in that high-entropy alloy powder is by Fe, Ni, Cr, Al, Cu
FeNiCrAlCuMnx, mol ratio and its span that x is Mn are expressed as with Mn element powders composition, i.e. alloy powder composition
It is equimolar ratio for 0.5-0.7, between described Fe, Ni, Cr, Al, Cu；By high-entropy alloy powder and ethanol in laser melting coating
After mixing, be coated uniformly on substrate material surface, cladding layer can be obtained by laser melting coating after drying, improve microhardness and
Anti-wear performance；In high-entropy alloy powder and alcohol mixture, according to mass percent by 92~95% alloy powder and 5~
8% ethanol composition；It is 42CrMo steel from matrix material when carrying out laser melting coating, technological parameter is：Laser power is
1550~1650KW, spot diameter is 0.8~1.0mm, and sweep speed is 150~200mm/min, and defocusing amount is 0mm, protects gas
Body uses argon gas or helium, and gas flow is 20~25L/min.
2. application of the high-entropy alloy powder according to claim 1 in laser melting coating, it is characterised in that select each group
It is powder of the purity more than or equal to 99% to divide, and particle diameter is 100-500 mesh.
3. application of the high-entropy alloy powder according to claim 1 in laser melting coating, it is characterised in that select each group
It is powder of the purity more than or equal to 99% to divide, and particle diameter is 200-300 mesh.
4. application of the high-entropy alloy powder according to claim 1 in laser melting coating, it is characterised in that in high-entropy alloy
Powder and ethanol mixing after, formed pasty state, in order to substrate material surface continue coat, it is coated after in substrate material surface
Preformed layer is formed, the preformed layer thickness is 1-2mm.
5. application of the high-entropy alloy powder according to claim 1 in laser melting coating, it is characterised in that carrying out laser
During cladding, preferably laser power is 1580~1620KW, and spot diameter is 0.8~1.0mm, and sweep speed is 180~200mm/
Min, defocusing amount is 0mm, and protective gas uses argon gas, and gas flow is 22~25L/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511016637.0A CN105401042B (en) | 2013-10-10 | 2013-10-10 | Application of the high-entropy alloy powder in laser melting coating |
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| CN201511016637.0A CN105401042B (en) | 2013-10-10 | 2013-10-10 | Application of the high-entropy alloy powder in laser melting coating |
| CN201310471107.XA CN104141127B (en) | 2013-10-10 | 2013-10-10 | Preparation method of high-entropy alloy powder and cladding layer and application |
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| CN105525232B (en) * | 2016-02-17 | 2017-08-08 | 西南交通大学 | It is a kind of for high-entropy alloy amorphous powder of 3D printing and preparation method thereof |
| CN105862035A (en) * | 2016-06-25 | 2016-08-17 | 芜湖三刀材料科技有限公司 | High-entropy alloy coating and preparation method thereof |
| CN105950946B (en) * | 2016-07-01 | 2017-11-21 | 广西大学 | A kind of method that high-entropy alloy composition design is carried out based on segregation situation between constituent element |
| CN107299342A (en) * | 2017-07-05 | 2017-10-27 | 暨南大学 | A kind of high-entropy alloy coating and its production and use |
| CN107699770B (en) * | 2017-08-21 | 2019-05-14 | 昆明理工大学 | A kind of high entropy alloy material and preparation method thereof |
| CN109797390A (en) * | 2017-11-17 | 2019-05-24 | 天津大学 | A kind of iron-based high-entropy alloy powder of wind power bearing and its cladding layer preparation method |
| CN108130502B (en) * | 2017-12-26 | 2020-08-25 | 湖南大学 | Preparation method and device of composite material containing high-entropy alloy coating |
| CN108359977B (en) * | 2018-04-11 | 2020-07-14 | 昆明理工大学 | FeCoVWNbSc high-entropy alloy powder for laser cladding and use method |
| CN111168053B (en) * | 2018-10-23 | 2021-08-24 | 天津大学 | Preparation method of raw material powder for high-entropy alloy selective laser melting additive manufacturing |
| TWI680209B (en) | 2018-12-28 | 2019-12-21 | 財團法人工業技術研究院 | Multicomponent alloy coating |
| CN110306099A (en) * | 2019-08-06 | 2019-10-08 | 鞍钢股份有限公司 | Low-cost high-entropy alloy and preparation method thereof |
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| CN111318805B (en) * | 2020-02-14 | 2022-03-22 | 江苏大学 | Laser welding method for high-entropy alloy with preset powder |
| TWI734605B (en) * | 2020-09-04 | 2021-07-21 | 國立中央大學 | High entropy nanomaterial and preparation method thereof |
| CN113293368A (en) * | 2021-05-21 | 2021-08-24 | 贵州大学 | High-hardness high-wear-resistance high-entropy intermetallic compound coating and preparation method thereof |
| CN114032437B (en) * | 2021-11-15 | 2022-09-23 | 海南大学 | Novel Fe-Cr-Co-Cu-Ti-Y multi-element high-entropy alloy coating and preparation method thereof |
| CN114939654B (en) * | 2022-05-27 | 2023-04-07 | 中机新材料研究院(郑州)有限公司 | High-entropy alloy powder for laser additive manufacturing and preparation method and application thereof |
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| JP2000153392A (en) * | 1998-11-18 | 2000-06-06 | Daido Steel Co Ltd | Sintering material for cladding by welding, and its manufacture |
| CN100491570C (en) * | 2006-08-21 | 2009-05-27 | 清华大学 | High-temperature alloy with low content of cobalt and nickel |
| CN101386928B (en) * | 2008-10-24 | 2011-04-06 | 昆明理工大学 | Method for preparing high-entropy alloy containing immiscible element |
| CN102796933A (en) * | 2012-09-04 | 2012-11-28 | 四川大学 | High-entropy alloy binder phase-based nitrogen-containing hard alloy and preparation method thereof |
| CN103060725A (en) * | 2013-01-22 | 2013-04-24 | 上海交通大学 | Nickel-base amorphous alloy powder as well as nickel-base amorphous composite coating and preparation method thereof |
| CN103290404B (en) * | 2013-05-06 | 2015-11-18 | 浙江工业大学 | The preparation method of laser melting coating high-entropy alloy powder and high-entropy alloy coating |
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| CN104141127B (en) | 2017-02-08 |
| CN104141127A (en) | 2014-11-12 |
| CN105401042A (en) | 2016-03-16 |
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