CN106065450A - A kind of high-entropy alloy powder and utilize the method that laser prepares cladding layer - Google Patents
A kind of high-entropy alloy powder and utilize the method that laser prepares cladding layer Download PDFInfo
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- CN106065450A CN106065450A CN201610613355.7A CN201610613355A CN106065450A CN 106065450 A CN106065450 A CN 106065450A CN 201610613355 A CN201610613355 A CN 201610613355A CN 106065450 A CN106065450 A CN 106065450A
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- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 96
- 239000000843 powder Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005253 cladding Methods 0.000 title claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007605 air drying Methods 0.000 claims description 11
- 238000004372 laser cladding Methods 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000005728 strengthening Methods 0.000 abstract description 5
- 238000005275 alloying Methods 0.000 abstract description 4
- 230000033001 locomotion Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000013532 laser treatment Methods 0.000 abstract 1
- 238000003701 mechanical milling Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
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- 239000007769 metal material Substances 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 230000002929 anti-fatigue Effects 0.000 description 1
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- 239000008199 coating composition Substances 0.000 description 1
- 230000005492 condensed matter physics Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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Classifications
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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
-
- 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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- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a kind of high-entropy alloy powder (i.e. CrFeNiTiMo), be made up of Cr, Fe, Ni, Ti, Mo element powders, additionally provide the method that described high-entropy alloy powder utilizes laser to prepare cladding layer simultaneously, carry out ball milling step including to described high-entropy alloy powder；Matrix is carried out pre-treatment step；Prepare initialization layer；Finally use laser instrument to carry out the preparation of cladding layer, all protect with Ar at whole mechanical milling process and laser treatment process.Cladding layer hardness prepared by the high-entropy alloy powder in the present invention significantly improves, reach Vickers hardness 800HV, Mo in alloying element is very effective solution strengthening element, can crystal grain thinning, the existence of Mo element is effectively increased the solute atoms quantity of solid solution, there is reciprocal action in solute atoms and dislocation, adds dislocation motion resistance, makes alloy strength improve；Thick atom radius Ti element is easily generated distortion of lattice, produces substantial amounts of solid solution, and solution strengthening effect is obvious.
Description
Technical field
The present invention relates to high-entropy alloy and cladding layer preparation method field thereof, specifically, be by Cr, Fe, Ni, Ti, Mo
Element powders composition high-entropy alloy powder and the preparation method of laser cladding layer thereof in five.
Background technology
Traditional alloy all with one or both (such as Fe, Al, Mg, Ni, Co, Cu etc.) metals as major components, alloy
Structure and performance depend primarily on major components.Along with the continuous progress of science and technology, the requirement to material is more and more higher, existing
Alloy can not meet and has been actually needed.
The class novel alloy material that high-entropy alloy develops the most under this background, high-entropy alloy is also known as high chaotic
Degree alloy, is to be taken the lead in breaking traditions in the nineties in 20th century alloy design pattern by China's Taiwan's scholars, and the new alloy of proposition sets
Meter theory, owing to its entropy relatively conventional alloys is high, therefore claims high-entropy alloy.Different from conventional alloys are: high-entropy alloy refers to
Containing the alloy of multiple essential element, the most each essential element has high molar fraction, but less than 35%, this alloy
It is to be embodied by multiple element collective and show its characteristic, such microstructure of the alloy simple in construction, even there will be amorphous phase and nanometer
Phase, alloy has excellent combination property, thus becomes a new research in material science and Condensed Matter Physics field
Focus.
Existing common high-entropy alloy has the most luxuriant face-centered cubic solid solution with CoCrCuFeNi as representative waiting discovery of leaf
The alloy of structure；The alloy of the body center cubic solid solution structure with AlCoCrFeNi as representative that Zhang Yong etc. find, but along with height
The development of entropy alloy material and constantly experiment, now need that hardness is more preferable, corrosion resistance strong, yield strength and fracture strong
Spend higher high-entropy alloy.
Summary of the invention
It is an object of the invention to provide a kind of high-entropy alloy powder, for improving existing metal material by laser melting coating means
Wearability, hardness and the intensity index of material；The present invention also provides for a kind of high-entropy alloy powder and utilizes laser to prepare cladding layer simultaneously
Method, for carrying out surface process to current material, it is thus achieved that high rigidity, the metal material of alkali resistance corrosive nature, to meet such as
Turbine, bearing etc. work in certain circumstances, manufacture the part that material hardness, requirement of strength are high.
The present invention is achieved through the following technical solutions:
A kind of high-entropy alloy powder, i.e. CrFeNiTiMo, be made up of Cr, Fe, Ni, Ti, Mo element powders, each element powders grain
Degree scope is 200-300 mesh, and the purity of each element powders is all higher than equal to 99.9%, the mol ratio of described Cr, Fe, Ni, Ti, Mo
For (1～1.05): (1～1.05): (1～1.05): (0.1～1.5): (0.1～1.5).
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:1:1.
A kind of high-entropy alloy powder utilizes the method that laser prepares cladding layer, comprises the steps of:
Described high-entropy alloy powder is put in ball mill by step 3.1, utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 3.2, and the concrete step that processes is followed successively by cleaning, is dried, polishes, refines and checks slightly
Rugosity, as roughness Ra ＜ 1.6, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural wind
Dry more than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 3.1 is completed by step 3.3 carries out moistening also
Stirring, evenly laid out on matrix surface, tiling thickness is that 0.8-1.2mm forms initialization layer, carries out natural air drying stand-by；Preferably
Ground, described initialization layer is 0.8-0.9mm, more preferably 0.8mm.
The initialization layer being dried in step 3.3 is used laser instrument to carry out Laser Cladding Treatment by step 3.4, described laser instrument
Hot spot is adjusted to circular light spot, spot diameter D=3.5-4.5mm, power P=2.2-2.6KW, scanning speed v=4-5mm/s, melts
The whole process covered uses Ar gas shielded.
Preferably, the initial speed of ball mill described in described step 3.1 is 200 revs/min, and Ball-milling Time often reaches 1 hour
Corresponding rotating speed increases by 50 revs/min, the highest is less than 500 revs/min.
Preferably, during matrix described in described step 3.3 is 40Cr steel, 42CrMo, 45 steel any one.
Preferably, laser instrument described in described step 3.4 is high power CO2Laser instrument.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the cladding layer hardness prepared by the high-entropy alloy powder in the present invention is significantly improved, and reaches Vickers hardness
800HV, meanwhile, in the present invention, the Mo in alloying element is very effective solution strengthening element, can crystal grain thinning, Mo element
There is the solute atoms quantity being effectively increased solid solution, there is reciprocal action, adds dislocation motion in solute atoms and dislocation
Resistance, makes alloy strength improve；Thick atom radius Ti element is easily generated distortion of lattice, produces substantial amounts of solid solution, solution strengthening
Effect is substantially.
(2) in the present invention, corrosion resistance to high-entropy alloy cladding layer significantly improves, thick atom radius Mo unit in the present invention
Element and Ti element make distortion of lattice aggravate, and cause grain boundaries to have higher energy, become corrosion-prone position.Ti element is originally
The corrosion resistant alloy corrosion resistance coating that body has excellence is good.Ti element can form the oxidation of densification in 1mol/L NaOH solution
Film, plays a good protection to internal alloy coat.
Accompanying drawing explanation
Fig. 1 is the tempering hardness curve chart of the embodiment of the present invention 4；
Fig. 2 is embodiment of the present invention 1-6 at the hardness profile of 880 degrees Celsius；
Fig. 3 is present invention corrosion current curve chart in 1mol/L NaOH solution；
Fig. 4 is present invention corrosion potential curve chart in 1mol/L NaOH solution；
Fig. 5 is the cladding layer thickness graph of relation with hardness of the embodiment of the present invention 4；
Fig. 6 is the high-entropy alloy XRD figure spectrum of the embodiment of the present invention 4 and embodiment 5；
Fig. 7 is high-entropy alloy CrFeNiTiMo microscopic structure in the present invention；
Fig. 8 is Cr elemental map in CrFeNiTiMo high-entropy alloy；
Fig. 9 is Fe elemental map in CrFeNiTiMo high-entropy alloy；
Figure 10 is Ni elemental map in CrFeNiTiMo high-entropy alloy；
Figure 11 is Ti elemental map in CrFeNiTiMo high-entropy alloy；
Figure 12 is Mo elemental map in CrFeNiTiMo high-entropy alloy.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Shown in accompanying drawing 1-12, carry out for matrix material with 40Cr steel, embodiment relate to explanation of nouns as follows:
Atomic ratio: the number ratio of Elements Atom in compound.
Mol ratio: " amount of material " is the number representing material, but it counts with number, if material is point
Son it refer to the number of molecule, if material is atom, it just refers to the number of atom, but a molecule or an atom pair
Our the most not use, the most abstract, the most nonsensical, the most just use a bigger number, Ah
Fu Jiadeluo constant (mole constant): six 02 are multiplied by 20 cube of ten.1 mole of something just has the most numbers
Atom or molecule.The quality of 1 mole of something is the most just its so much gram of molecular weight.If 1 mole of S is 32g, 1 mole of N2
It is 28g.
Molar fraction: the amount sum of the amount of the material of a kind of material in mixture or solution and the material of each component it
Ratio, is the molar fraction of this component.
Entropy: the degree of " out of order " in a system, also characterizes a kind of tolerance of vital movement procedure quality.
Constituent element: independent, the most basic unit of component alloy is referred to as constituent element, constituent element can be component alloy element or
Stable compound.
Embodiment 1:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:0.2:
0.2。
Embodiment 2:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:0.5:
0.5。
Embodiment 3:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:
0.75:0.75.
Embodiment 4:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:1:1.
Embodiment 5:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:
1.25:1.25.
Embodiment 6:
A kind of high-entropy alloy powder, is made up of Cr, Fe, Ni, Ti, Mo element powders, and each element powders particle size range is 200-
300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is 1:1:1:1.5:
1.5。
Embodiment 7:
High-entropy alloy powder described in embodiment 1-6 is carried out the most as steps described below laser melting coating test:
Described high-entropy alloy powder is put in ball mill by step 1., utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 2., and the concrete step that processes is followed successively by cleaning, is dried, polishes, refines and checks slightly
Rugosity, when roughness Ra=0.3, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural wind
Dry more than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 1 is completed by step 3. carries out moistening and stirs
Mixing, evenly laid out on matrix surface, tiling thickness is that 0.8mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3 is used laser instrument to carry out Laser Cladding Treatment, the light of described laser instrument by step 4.
Speckle is adjusted to circular light spot, spot diameter D=3.5mm, power P=2.5KW, scanning speed v=5mm/s, the whole process of cladding
Use Ar gas shielded.
Embodiment 8:
High-entropy alloy powder described in embodiment 4 is carried out the most as steps described below laser melting coating test:
Described high-entropy alloy powder is put in ball mill by step 1., utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 2., and the concrete step that processes is followed successively by cleaning, is dried, polishes, refines and checks slightly
Rugosity, when roughness Ra=1, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural air drying
More than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 1 is completed by step 3. carries out moistening and stirs
Mixing, evenly laid out on matrix surface, tiling thickness is that 0.8mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3 is used laser instrument to carry out Laser Cladding Treatment, the light of described laser instrument by step 4.
Speckle is adjusted to circular light spot, spot diameter D=3.5mm, power P=2.5KW, scanning speed v=5mm/s, the whole process of cladding
Use Ar gas shielded.
Embodiment 9:
High-entropy alloy powder described in embodiment 4 is carried out the most as steps described below laser melting coating test:
Described high-entropy alloy powder is put in ball mill by step 1., utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 2., and the concrete step that processes is followed successively by cleaning, is dried, polishes, refines and checks slightly
Rugosity, when roughness Ra=1.6, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural wind
Dry more than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 1 is completed by step 3. carries out moistening and stirs
Mixing, evenly laid out on matrix surface, tiling thickness is that 0.9mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3 is used laser instrument to carry out Laser Cladding Treatment, the light of described laser instrument by step 4.
Speckle is adjusted to circular light spot, spot diameter D=3.5mm, power P=2.5KW, scanning speed v=5mm/s, the whole process of cladding
Use Ar gas shielded.
Embodiment 10:
High-entropy alloy powder described in embodiment 4 is carried out the most as steps described below laser melting coating test:
Described high-entropy alloy powder is put in ball mill by step 1., utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 2., and the concrete step that processes is followed successively by cleaning, is dried, polishes, refines and checks slightly
Rugosity, when roughness Ra=3, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural air drying
More than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 1 is completed by step 3. carries out moistening and stirs
Mixing, evenly laid out on matrix surface, tiling thickness is that 1.2mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3 is used laser instrument to carry out Laser Cladding Treatment, the light of described laser instrument by step 4.
Speckle is adjusted to circular light spot, spot diameter D=3.5mm, power P=2.5KW, scanning speed v=5mm/s, the whole process of cladding
Use Ar gas shielded.
Embodiment 11:
High-entropy alloy powder described in embodiment 4 is carried out the most as steps described below laser melting coating test:
Described high-entropy alloy powder is put in ball mill by step 1., utilizes evacuator that ball mill is carried out vacuum drawn,
After vacuum reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 2., and the concrete step that processes is followed successively by cleaning, is dried and does not polishes, surface quality
Do not process, directly carry out surface clean with acetone, air-dry 10-15 minute, again clean with acetone, natural air drying more than 60 minutes
Stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 1 is completed by step 3. carries out moistening and stirs
Mixing, evenly laid out on matrix surface, tiling thickness is that 2.5mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3 is used laser instrument to carry out Laser Cladding Treatment, the light of described laser instrument by step 4.
Speckle is adjusted to circular light spot, spot diameter D=3.5mm, power P=2.5KW, scanning speed v=5mm/s, the whole process of cladding
Use Ar gas shielded.
The mol ratio change of Cr, Fe, Ni, Ti, Mo can be drawn as shown in table 1 from embodiment 1-embodiment 6:
Table 1
Each Elements Atom radius is as shown in table 2:
| Element | Cr | Fe | Ni | Ti | Mo |
| Atomic radius | 1.85 | 1.72 | 1.62 | 2.00 | 2.01 |
| Electronegativity | 1.66 | 1.83 | 1.91 | 1.54 | 2.16 |
Table 2
Be illustrated in figure 1 temperature and the curve linear relationship of corresponding hardness of the embodiment of the present invention 4, embodiment 1,2,3,5,
6 with the curve tendency of embodiment 4 approximation, maximum hardness is between 850 °-900 °, and maximum hardness value is less than embodiment 4
In maximum hardness value.
As in figure 2 it is shown, in embodiment 1-6 in the case of equal temperature 880 °, use the element mole of embodiment 4
More maximum than the maximum hardness value obtained.What deserves to be explained is: in the present invention, the Mo in alloying element is that very effective solid solution is strong
Change element, can crystal grain thinning, and there is heat resistance, in the present invention, the molar fraction of Mo element is about 20%, depositing of Mo element
Being effectively increased the solute atoms quantity of solid solution, there is reciprocal action in solute atoms and dislocation, adds dislocation motion resistance
Power, makes alloy strength improve；Thick atom radius Ti element is easily generated distortion of lattice, produces substantial amounts of solid solution, and solution strengthening is made
With substantially, these all serve important function to alloy coat hardness.
As shown in Figure 6, the intensity that in embodiment 1-6, the mol ratio in embodiment 4 obtains under equal x-ray bombardment angle
It is substantially better than and is positioned at the embodiment 5 taken second place.Through demarcating, this alloy is mainly stood by a kind of body-centered cubic structure BCC and a kind of center of area
Square structure FCC forms；XRD analysis shows, the number of phases formed in laser cladding layer is far smaller than and calculates gained according to Gibbs one after another
The number of phases, reason is that five kinds of elements of Cr, Fe, Ni, Ti, Mo mix the high entropic effect of generation and inhibit between complicated metal
The generation of compound.
As shown in Figure 3, Figure 4, according to carrying out laser melting coating examination according to step described in embodiment 7 respectively in embodiment 1-6
Test, the high-entropy alloy of acquisition is invaded respectively in 1mol/L NaOH solution, according to electrochemical principle, corrosion current (Icorr)
The least, corrosion potential (Ecorr) the highest, then corrosion resistance is the best, otherwise, corrosion resistance is the poorest.High-entropy alloy (CrFeNiTiMo) is coated with
Corrosion current reduction an order of magnitude compared with matrix 40Cr steel of layer, corrosion potential is shuffled compared with matrix 40Cr steel
0.33V.Show that the corrosion resistance of coating is remarkably reinforced.Corrosion resistance is relevant with the element kind in alloy coat and content, group simultaneously
Corrosion resistance is also had an impact by the uniformity knitted.
Shown in table 2, the atomic radius of Mo element is maximum in 5 kinds of elements, and Ti element takes second place, and atomic radius difference is more
Greatly, the distortion of lattice caused is the biggest so that the phenomenon of left shift occurs in diffraction maximum.
As it is shown in figure 5,7-embodiment 11 in conjunction with the embodiments, the mol ratio of the identical element in embodiment 4 is all used to carry out
Laser melting coating is tested, and its coating thickness is followed successively by 0.8mm, 0.8mm, 0.9mm, 1.2mm, 2.5mm, and coating thickness is gradually passed
Increasing, according to the relation of coating thickness in Fig. 5 Yu hardness, after coating thickness is more than 1.2mm, its hardness is slightly higher
In the intrinsic hardness of matrix 40Cr steel, performance is inconspicuous, and substantially decay occurs in hardness curve, and therefore coating thickness is preferred
Within 1.2mm.
Understand in sum:
Conclusion one, high-entropy alloy CrFeNiTiMo of the present invention are 20% when the molar fraction of Ti and Mo element
Time, hardness reaches peak value, all can decline, especially when rubbing when the molar fraction of Ti and/or Mo element increases or reduces its hardness
Your mark downward trend more than 20% is more obvious than the downward trend less than 20%, so Ti and Mo unit in preferred version of the present invention
The molar fraction of element is 20% deviation and controls within 0.5%.
In conclusion two, heretofore described laser cladding method between roughness and cladding layer and the matrix of matrix 40Cr steel
Element solid solution body have direct relation, the surface roughness of matrix 40Cr steel is the lowest, its element solid solution body formed the best, utilization is swept
Retouch the tissue topography of electron microscope observation high-entropy alloy, and with the micro-area composition of its subsidiary energy disperse spectroscopy beta alloy；Utilize X
X ray diffractometer x analyzes alloy thing phase composition, and condition is: Cu target, voltage 40kV, electric current 40mA, and scanning angle is 20 °-90 °, sweeps
Retouching speed is 4 °/min.
CrFeNiTiMo high-entropy alloy coating is mainly made up of equiax crystal, and that waits uranium crystalline substance is formed as melt inner crystalline core
Free growing result.In laser cladding process, there is not preferred orientation in the nucleus in centre, molten bath due to direction of heat flow, therefore
It is roughly equal to the speed of surrounding growth, thus forms equiax crystal.Fig. 7 is micro-group of CrFeNiTiMo high-entropy alloy coating
Knitting, Fig. 7 is carried out element Surface scan, result is shown in Fig. 8-Figure 12.Analysis shows, CrFeNiTiMo high-entropy alloy coating composition is equal
Even, the situation of component segregation does not occurs.
In the present invention, the addition of solid solution alloying elements Mo improves recrystallization temperature, and can reduce at a certain temperature
The speed that crystal grain is grown up, makes crystal grain refine.Meanwhile, in the present invention, Ti element can in molten bath in the case of laser high-energy injects
There is provided substantial amounts of dispersoid particle to promote Heterogeneous Nucleation, thus obtain more fine grain after solidification.Crystal grain is the thinnest, and it is comprehensive
Can be the best, and anti-fatigue performance is the highest.
Although the anti-look-down capability of the molar fraction of conclusion three Ti element its CrFeNiTiMo high-entropy alloy the highest is the strongest,
After the molar fraction of Ti element is more than 20%, the hardness of CrFeNiTiMo high-entropy alloy can reduce, it may appear that attends to one thing and lose sight of another
Situation, so, the hardness of comprehensive CrFeNiTiMo high-entropy alloy and the content of corrosion resistance, preferably Ti are 20%.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on
Any simple modification of being made above example according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (7)
1. a high-entropy alloy powder, it is characterised in that be made up of Cr, Fe, Ni, Ti, Mo element powders, each element powders granularity model
Enclosing for 200-300 mesh, the purity of each element powders is all higher than equal to 99.9%, and the mol ratio of described Cr, Fe, Ni, Ti, Mo is (1
～1.05): (1～1.05): (1～1.05): (0.1～1.5): (0.1～1.5).
A kind of high-entropy alloy powder the most according to claim 1, it is characterised in that the mol ratio of described Cr, Fe, Ni, Ti, Mo
For 1:1:1:1:1.
The method that a kind of high-entropy alloy powder the most according to claim 1 and 2 utilizes laser to prepare cladding layer, its feature exists
In, comprise the steps of:
Described high-entropy alloy powder is put in ball mill by step 3.1, utilizes evacuator that ball mill is carried out vacuum drawn, takes seriously
After reciprocal of duty cycle reaches below 5000Pa, injecting Ar gas and carry out ball milling, continuing Ball-milling Time is 6-8 hour；
Matrix is carried out pretreatment by step 3.2, concrete process step be followed successively by cleaning, be dried, polish, refine and check coarse
Degree, as roughness Ra ＜ 1.6, carries out surface clean with acetone, air-dries 10-15 minute, again cleans with acetone, natural air drying
More than 60 minutes stand-by；
The ethanol that high-entropy alloy powder purity is 90-95% that ball milling in step 3.1 is completed by step 3.3 carries out moistening and stirs,
Evenly laid out on matrix surface, tiling thickness is that 0.8-1.2mm forms initialization layer, carries out natural air drying stand-by；
The initialization layer being dried in step 3.3 is used laser instrument to carry out Laser Cladding Treatment, the hot spot of described laser instrument by step 3.4
It is adjusted to circular light spot, spot diameter D=3.5-4.5mm, power P=2.2-2.6KW, scanning speed v=4-5mm/s, cladding whole
Process uses Ar gas shielded.
The method that a kind of high-entropy alloy powder the most according to claim 3 utilizes laser to prepare cladding layer, it is characterised in that institute
The initial speed stating ball mill described in step 3.1 is 200 revs/min, Ball-milling Time often reach 1 hour corresponding rotating speed increase by 50 turns/
Point, the highest it is less than 500 revs/min.
The method that a kind of high-entropy alloy powder the most according to claim 3 utilizes laser to prepare cladding layer, it is characterised in that institute
State matrix be in 40Cr steel, 42CrMo, 45 steel any one.
The method that a kind of high-entropy alloy powder the most according to claim 3 utilizes laser to prepare cladding layer, it is characterised in that institute
Stating coating thickness in step 3.3 is 0.8mm or 0.9mm.
The method that a kind of high-entropy alloy powder the most according to claim 3 utilizes laser to prepare cladding layer, it is characterised in that institute
Stating laser instrument described in step 3.4 is high power CO2Laser instrument.
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| CN109112385A (en) * | 2018-09-18 | 2019-01-01 | 湘潭大学 | CrCuNiFeTiMo high entropy alloy material and preparation method thereof |
| CN109797391A (en) * | 2017-11-17 | 2019-05-24 | 天津大学 | A kind of preparation method of wind power bearing low dilution rate FeCrCoNiMoTi high-entropy alloy powder and its cladding layer |
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| CN109082659A (en) * | 2018-10-26 | 2018-12-25 | 河海大学常州校区 | A kind of preparation method applied to the metal coating under corrosive environment |
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| CN111593339A (en) * | 2020-04-21 | 2020-08-28 | 上海工程技术大学 | Multilayer high-entropy alloy laser cladding layer containing nano tantalum carbide and preparation method thereof |
| CN111593339B (en) * | 2020-04-21 | 2022-06-24 | 上海工程技术大学 | Multilayer high-entropy alloy laser cladding layer containing nano tantalum carbide and preparation method thereof |
| TWI734605B (en) * | 2020-09-04 | 2021-07-21 | 國立中央大學 | High entropy nanomaterial and preparation method thereof |
| CN115011147A (en) * | 2021-09-22 | 2022-09-06 | 武汉苏泊尔炊具有限公司 | Composite material and preparation method thereof, non-stick cooker and manufacturing method thereof |
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