CN104141085A - Six-element high-entropy alloy powder, laser cladding layer preparation method and application - Google Patents
Six-element high-entropy alloy powder, laser cladding layer preparation method and application Download PDFInfo
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- CN104141085A CN104141085A CN201310471070.0A CN201310471070A CN104141085A CN 104141085 A CN104141085 A CN 104141085A CN 201310471070 A CN201310471070 A CN 201310471070A CN 104141085 A CN104141085 A CN 104141085A
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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 a six-element high-entropy alloy powder, a laser cladding layer preparation method and application. The alloy powder composition is represented as FeNiCrAlSiCu, and the six metal elements are consistent in mole number. Firstly, blending calculation is carried out according to the mole ratio of each element, and after accurate weighing of the mass of each component, the components are thoroughly mixed evenly so as to obtain the six-element high-entropy alloy powder. The alloy powder provided by the invention can be applied to laser cladding welding, the six-element high-entropy alloy powder is mixed with ethanol, the mixture is employed for coating the surface of a matrix material evenly, and after drying performing laser cladding, thus obtaining a cladding layer. The high-entropy alloy powder provided according to the technical scheme of the invention is composed of metallic and non-metallic elements, the self-fluxing of the powder is improved, the cladding layer with good shape, high hardness and good wear resistance can be prepared, and the performance is obviously improved compared with the matrix.
Description
Technical field
The present invention relates to high-entropy alloy powder and cladding layer preparation field for many pivots laser melting coating, more particularly, relate to hexa-atomic high-entropy alloy powder and laser cladding layer preparation method and application.
Background technology
Many pivots high-entropy alloy is a kind of novel alloy that last century, the nineties was proposed by China Taiwan's scholars professor Ye Junwei, high-entropy alloy is different from take single-element as main conventional alloys, it is elementary composition by 5～13 kinds, the molar fraction of every kind of element is between 5%～35%, and its performance is determined by multiple pivot acting in conjunction.The proposition of this kind of alloy designs theory, having broken conventional alloys single element is main design philosophy, has opened a new alloy designs field.Because high-entropy alloy presents the good characteristic that a lot of conventional alloys do not possess, the excellent specific properties such as, high temperature oxidation resisting softening, corrosion-resistant such as high rigidity, high work hardening, high temperature resistance, can be applicable to high temperature material, chemical industry, naval vessel corrosion resistant material, the heat-stable material of aircraft turbine blades, High Temperature Furnaces Heating Apparatus, has great application prospect.
At present, existing by adopting the method for galvanic deposit and magnetron sputtering to prepare high-entropy alloy coating, but the coating obtaining by these methods is too thin, can not meet heavy-duty applications occasion.Laser melting coating has high heating and cooling speed, and coating and matrix are metallurgical binding, and bonding strength is high, and coat-thickness reaches as high as several millimeters.In addition, the rapid solidification feature of laser melting coating can make alloy structure refinement, thereby obtains higher hardness and wear resisting property.But at present less about the research of laser melting coating high-entropy alloy coating, also in the starting stage.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of high-entropy alloy powder material and cladding layer preparation method are provided, obtain the good cladding layer that is shaped, improve material hardness and wear resistance.
Technical purpose of the present invention is achieved by following technical proposals:
Hexa-atomic high-entropy alloy powder, Fe, Ni, Cr, Al, Si and Cu element powders, consist of, powdered alloy composition is expressed as FeNiCrAlSiCu, specifically, between described Fe, Ni, Cr, Al, Si and Cu, be equimolar ratio, the mole number of six kinds of metallic element uses is consistent.
When being prepared, first according to the mol ratio of element separately, carry out proportioning calculating, accurately after the quality of each component of weighing, carried out fully mixing with evenly, for example, adopt electronic scale to take the powder of various elements, in mortar, grind and make half an hour it mix.Wherein select each component to be purity and be more than or equal to 99% powder, particle diameter is 100-500 orders, preferably 200-300 orders.
Utilize powdered alloy of the present invention to be applied in laser melting coating welding, by after hexa-atomic high-entropy alloy powder and ethanol mixing, be evenly coated in substrate material surface, after being dried, by laser melting coating, can obtain cladding layer.
The pure dehydrated alcohol of wherein said ethanol Analysis about Selection, in hexa-atomic high-entropy alloy powder and alcohol mixture, is comprised of 92～95% powdered alloy and 5～8% ethanol according to mass percent.
After mixing, form pasty state or paste, so that continue to apply at substrate material surface, after applying, at substrate material surface, form preformed layer, described preformed layer thickness is 1-2mm.
When carrying out laser melting coating, selecting body material is 42CrMo steel, and processing parameter is: laser power is 1550～1650KW, spot diameter is 0.8～1.0mm, and sweep velocity is 150～200mm/min, and defocusing amount is 0mm, shielding gas adopts argon gas or helium, and gas flow is 20～25L/min; Preferably laser power is 1580～1620KW, and spot diameter is 0.8～1.0mm, and sweep velocity is 180～200mm/min, and defocusing amount is 0mm, and shielding gas adopts argon gas, and gas flow is 22～25L/min.
Compared with prior art, tool of the present invention has the following advantages:
(1) in powdered alloy of the present invention, remove the maximum performance of giving full play to each element outside fundamental element iron, Ni is mainly used in improving material wettability and improves cladding layer capability, Cr mainly improves cladding layer hardness by solution strengthening and for improving cladding layer solidity to corrosion, Al mainly improves the high temperature oxidation resistance of cladding layer, and improves cladding layer hardness by solution strengthening effect and increase Grain Boundary Sliding resistance.In addition, because aluminium surface is very easily oxidized, form fine and close oxide film, add the solidity to corrosion that Al can also improve cladding layer in alloy, Si is mainly used in deoxidation, and Cu is mainly used in improving cladding layer wear resistance.
(2) the invention provides a kind of high-entropy alloy powder jointly being formed by metallic element and non-metallic element, improved the self-fluxing nature of powder.
(3) the present invention prepared be shaped good, hardness is higher, the good cladding layer of wear resistance, performance has had obvious improvement compared with base material.
Accompanying drawing explanation
Fig. 1 is FeNiCrAlSiCu cladding layer macro morphology.
Fig. 2 is FeNiCrAlSiCu cladding layer overall picture.
Fig. 3 is the metallographic structure of FeNiCrAlSiCu cladding layer.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.Each metallic element source is as shown in the table:
| Nomenclature of drug | Molecular formula | Purity | Specification | Manufacturer |
| Iron powder | Fe | ≥99% | Analytical pure | Tianjin chemical reagent one factory |
| Chromium powder | Cr | ≥99% | Analytical pure | Tianjin recovery fine chemistry industry institute |
| Nickel powder | Ni | ≥99.5% | Analytical pure | Tianmen, Hubei chemical reagent two factories |
| Aluminium powder | Al | ≥99% | Analytical pure | Tianjin Feng Chuan chemical reagent company limited |
| Silica flour | Si | ≥99% | Analytical pure | Tianjin recovery fine chemistry industry institute |
| Copper powder | Cu | ≥99.5% | Analytical pure | Ke Wei company of University Of Tianjin |
Body material is selected 42CrMo steel, adopts mechanical grinding to remove oxide compound, adopts acetone wipe oil, and its chemical composition is as shown in following table (massfraction %):
| 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 |
Implement by the following method:
1. according to mol ratio, carry out FeNiCrAlCuMn high-entropy alloy powder proportioning and calculate, adopt electronic scale to take the powder of various elements, in mortar, grind and make half an hour it mix.
2. the ethanol of 92～95% laser cladding powder and 5～8% is mixed into after pasty state or paste, is coated in substrate material surface, preformed layer thickness is 1-2mm, can obtain cladding layer after air-dry by laser melting coating.
3. select laser apparatus to adopt JK2003SM type Nd:YAG to carry out laser melting coating.
4. metallographic structure facilities for observation adopts OLYMPUS-GX51 metaloscope, manufacturer: Japanese OLYMPUS(Olympus) company.
Case study on implementation 1
1. according to mol ratio, carrying out FeNiCrAlSiCu high-entropy alloy powder proportioning calculates: Fe is 16.67mol%, Ni is 16.67mol%, Cr is 16.67mol%, Al is 16.67mol%, Si is 16.66mol%, Cu is 16.66mol%, and total mol ratio is 100%, and adopts electronic scale to take the powder of various elements.
2. pour mortar into, in mortar, grind and make half an hour it mix.
3. by the laser cladding powder preparing, 92% and 8% ethanol is mixed into after pasty state or paste, is coated in 42CrMo steel surface, and coating thickness is 1mm, carries out laser melting coating after air-dry.
4. laser cladding technological parameter is: laser power is 1550KW, and spot diameter is 0.8mm, and sweep velocity is 180mm/min, and defocusing amount is 0mm, and shielding gas adopts argon gas, and gas flow is 25L/min.
5. after laser melting coating, adopt chloroazotic acid to corrode, obtained the metallograph of cladding layer.
Adopt automatic turret digital display sclerometer to measure the microhardness of cladding layer, experimental result is as shown in the table, and after laser melting coating, average hardness has reached 523.3HV, than mother metal, significantly improves.
| ? | Hardness value | Hardness value 2 | Hardness value 3 | Average hardness |
| Mother metal | 286HV | 282HV | 285HV | 284HV |
| FeNiCrAlSiCu cladding layer | 520.8HV | 523.8HV | 525.2HV | 523.3HV |
Its wear resistance that adopted MM-200 type determination of wear testing machine, specimen size is 7 * 7 * 25mm, and friction duty, for dry grinding sliding friction, is loaded as 5kg, and rotating speed is 200r/min, and experimental period is 1h; Quality (cleaning with ultrasonic washing instrument before measuring) before and after measuring with electronic scale, experimental result is as shown in the table.Can find out, the weightlessness of mother metal is 11.49 times of cladding layer, compares with mother metal, and the wear resistance of cladding layer significantly improves.
| ? | Quality/g before wearing and tearing | Quality/g before wearing and tearing | Weightlessness/mg |
| Mother metal | 9.0479 | 9.0008 | 47.1 |
| FeNiCrAlSiCu cladding layer | 9.2616 | 9.2575 | 4.1 |
Case study on implementation 2
1. by the laser cladding powder preparing, 95% and 5% ethanol is mixed into after pasty state or paste, is coated in 42CrMo steel surface, and coating thickness is 2mm, carries out laser melting coating after air-dry.
2. laser cladding technological parameter is: laser power is 1650KW, and spot diameter is 1.0mm, and sweep velocity is 200mm/min, and defocusing amount is 0mm, and shielding gas adopts helium, and gas flow is 20L/min.
3. adopt the identical performance test of carrying out, result is as shown in the table:
Case study on implementation 3
1. by the laser cladding powder preparing, 94% and 6% ethanol is mixed into after pasty state or paste, is coated in 42CrMo steel surface, and coating thickness is 1.5mm, carries out laser melting coating after air-dry.
2. laser cladding technological parameter is: laser power is 1620KW, and spot diameter is 0.9mm, and sweep velocity is 180mm/min, and defocusing amount is 0mm, and shielding gas adopts argon gas, and gas flow is 22L/min.
3. adopt the identical performance test of carrying out, result is as shown in the table:
Case study on implementation 4
1. by the laser cladding powder preparing, 93% and 7% ethanol is mixed into after pasty state or paste, is coated in 42CrMo steel surface, and coating thickness is 1mm, carries out laser melting coating after air-dry.
2. laser cladding technological parameter is: laser power is 1580KW, and spot diameter is 0.8mm, and sweep velocity is 150mm/min, and defocusing amount is 0mm, and shielding gas adopts helium, and gas flow is 20L/min
3. adopt the identical performance test of carrying out, result is as shown in the table:
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (9)
1. hexa-atomic high-entropy alloy powder, is characterized in that, Fe, Ni, Cr, Al, Si and Cu element powders, consists of, and powdered alloy composition is expressed as FeNiCrAlSiCu, is equimolar ratio between described Fe, Ni, Cr, Al, Si and Cu.
2. hexa-atomic high-entropy alloy powder according to claim 1, is characterized in that, selects each component to be purity and is more than or equal to 99% powder, and particle diameter is 100-500 orders, preferably 200-300 orders.
3. one kind is utilized hexa-atomic high-entropy alloy powder as claimed in claim 1 to prepare the method for cladding layer, it is characterized in that, by after hexa-atomic high-entropy alloy powder and ethanol mixing, evenly be coated in substrate material surface, after dry, by laser melting coating, can obtain cladding layer, in hexa-atomic high-entropy alloy powder and alcohol mixture, according to mass percent, by 92～95% powdered alloy and 5～8% ethanol, formed.
4. the method for preparing cladding layer according to claim 3, is characterized in that, the pure dehydrated alcohol of described ethanol Analysis about Selection.
5. the method for preparing cladding layer according to claim 3, it is characterized in that, after hexa-atomic high-entropy alloy powder and ethanol mixing, form pasty state or paste, so that continue to apply at substrate material surface, after applying, at substrate material surface, form preformed layer, described preformed layer thickness is 1-2mm.
6. the method for preparing cladding layer according to claim 3; it is characterized in that; when carrying out laser melting coating; selecting body material is 42CrMo steel, and processing parameter is: laser power is 1550～1650KW, and spot diameter is 0.8～1.0mm; sweep velocity is 150～200mm/min; defocusing amount is 0mm, and shielding gas adopts argon gas or helium, and gas flow is 20～25L/min.
7. the method for preparing cladding layer according to claim 3; it is characterized in that; when carrying out laser melting coating; selecting body material is 42CrMo steel, and processing parameter is: preferably laser power is 1580～1620KW, and spot diameter is 0.8～1.0mm; sweep velocity is 180～200mm/min; defocusing amount is 0mm, and shielding gas adopts argon gas, and gas flow is 22～25L/min.
8. the application of hexa-atomic high-entropy alloy powder as claimed in claim 1 in laser melting coating, and improve microhardness and wear resisting property.
9. the application of hexa-atomic high-entropy alloy powder according to claim 8 in laser melting coating,, it is characterized in that, selecting body material is 42CrMo steel.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310471070.0A CN104141085B (en) | 2013-10-10 | 2013-10-10 | Hexa-atomic high-entropy alloy powder and laser cladding layer preparation method and application |
| CN201511015607.8A CN105441771B (en) | 2013-10-10 | 2013-10-10 | Application of the hexa-atomic alloy powder in laser melting coating |
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| CN201310471070.0A CN104141085B (en) | 2013-10-10 | 2013-10-10 | Hexa-atomic high-entropy alloy powder and laser cladding layer preparation method and application |
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| CN201511015607.8A Expired - Fee Related CN105441771B (en) | 2013-10-10 | 2013-10-10 | Application of the hexa-atomic alloy powder in laser melting coating |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313572A (en) * | 2014-11-14 | 2015-01-28 | 重庆理工大学 | Preparation method for Al-Cr-Ti-Si-Cu multi-principal element laser alloying coating on surface of aluminum alloy |
| CN104451351A (en) * | 2014-12-25 | 2015-03-25 | 安徽工业大学 | Method for improving toughness of boracic high-entropy alloy by adding rare earth |
| CN105088005A (en) * | 2015-08-13 | 2015-11-25 | 山西玉华再制造科技有限公司 | Non-spark aluminum bronze powder for laser cladding, preparation method and cladding method |
| CN105331870A (en) * | 2015-11-30 | 2016-02-17 | 重庆理工大学 | Multi-principal element alloy containing trace B and method for surface treatment of titanium alloy |
| CN105401114A (en) * | 2015-11-18 | 2016-03-16 | 郑郧 | Method for preparing multi-principal element alloy coating on titanium alloy surface |
| CN105568335A (en) * | 2015-09-24 | 2016-05-11 | 江门职业技术学院 | Technology of preparing FeNiCoCuCr high-entropy alloy coating on steel base material surface |
| 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 |
| CN105950947A (en) * | 2016-07-06 | 2016-09-21 | 浙江亚通焊材有限公司 | Iron-rich high-entropy alloy powder material for 3D printing and preparation method thereof |
| CN106756636A (en) * | 2016-11-28 | 2017-05-31 | 西安交通大学 | A kind of anti-corrosion amorphous high-entropy alloy high and preparation method thereof |
| CN109648166A (en) * | 2017-10-10 | 2019-04-19 | 沈阳金研激光再制造技术开发有限公司 | A kind of preparation method of the big thickness high hardness spray coating of titanium alloy |
| CN109913717A (en) * | 2019-04-04 | 2019-06-21 | 西安交通大学 | A kind of lightweight high-entropy alloy and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104313572A (en) * | 2014-11-14 | 2015-01-28 | 重庆理工大学 | Preparation method for Al-Cr-Ti-Si-Cu multi-principal element laser alloying coating on surface of aluminum alloy |
| CN104313572B (en) * | 2014-11-14 | 2017-10-03 | 重庆理工大学 | A kind of preparation method of aluminum alloy surface laser alloying Al Cr Ti Si Cu multi-principal elements alloy coatings |
| CN104451351A (en) * | 2014-12-25 | 2015-03-25 | 安徽工业大学 | Method for improving toughness of boracic high-entropy alloy by adding rare earth |
| CN105088005A (en) * | 2015-08-13 | 2015-11-25 | 山西玉华再制造科技有限公司 | Non-spark aluminum bronze powder for laser cladding, preparation method and cladding method |
| CN105568335A (en) * | 2015-09-24 | 2016-05-11 | 江门职业技术学院 | Technology of preparing FeNiCoCuCr high-entropy alloy coating on steel base material surface |
| CN105401114B (en) * | 2015-11-18 | 2017-11-14 | 郑郧 | A kind of method that titanium alloy surface prepares multi-principal elements alloy coating |
| CN105401114A (en) * | 2015-11-18 | 2016-03-16 | 郑郧 | Method for preparing multi-principal element alloy coating on titanium alloy surface |
| CN105331870B (en) * | 2015-11-30 | 2017-04-12 | 重庆理工大学 | Multi-principal element alloy containing trace B and method for surface treatment of titanium alloy |
| CN105331870A (en) * | 2015-11-30 | 2016-02-17 | 重庆理工大学 | Multi-principal element alloy containing trace B and method for surface treatment of titanium alloy |
| 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 |
| CN105950947A (en) * | 2016-07-06 | 2016-09-21 | 浙江亚通焊材有限公司 | Iron-rich high-entropy alloy powder material for 3D printing and preparation method thereof |
| CN106756636A (en) * | 2016-11-28 | 2017-05-31 | 西安交通大学 | A kind of anti-corrosion amorphous high-entropy alloy high and preparation method thereof |
| CN109648166A (en) * | 2017-10-10 | 2019-04-19 | 沈阳金研激光再制造技术开发有限公司 | A kind of preparation method of the big thickness high hardness spray coating of titanium alloy |
| CN109648166B (en) * | 2017-10-10 | 2021-01-29 | 沈阳金研激光再制造技术开发有限公司 | Preparation method of titanium alloy large-thickness high-hardness coating |
| CN109913717A (en) * | 2019-04-04 | 2019-06-21 | 西安交通大学 | A kind of lightweight high-entropy alloy and preparation method thereof |
| CN113005349A (en) * | 2021-02-24 | 2021-06-22 | 沈阳工业大学 | Fe-Cr-Ni-Cu-Al high-damping high-entropy alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104141085B (en) | 2017-01-04 |
| CN105441771B (en) | 2018-07-13 |
| CN105441771A (en) | 2016-03-30 |
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