CN106756642A - A kind of strong glass forming ability Fe-based amorphous alloy and the high-compactness amorphous alloy coating of resistance to long-term corrosion - Google Patents
A kind of strong glass forming ability Fe-based amorphous alloy and the high-compactness amorphous alloy coating of resistance to long-term corrosion Download PDFInfo
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- CN106756642A CN106756642A CN201611190659.3A CN201611190659A CN106756642A CN 106756642 A CN106756642 A CN 106756642A CN 201611190659 A CN201611190659 A CN 201611190659A CN 106756642 A CN106756642 A CN 106756642A
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 84
- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000005260 corrosion Methods 0.000 title claims abstract description 42
- 230000007797 corrosion Effects 0.000 title claims abstract description 40
- 238000007496 glass forming Methods 0.000 title claims abstract description 16
- 230000007774 longterm Effects 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000956 alloy Substances 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000010286 high velocity air fuel Methods 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 9
- 238000009689 gas atomisation Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000010962 carbon steel Substances 0.000 claims abstract description 6
- 239000005300 metallic glass Substances 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 19
- 239000007921 spray Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010285 flame spraying Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- 239000002737 fuel gas Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 238000000889 atomisation Methods 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 238000000634 powder X-ray diffraction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 235000019580 granularity Nutrition 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910000604 Ferrochrome Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910015136 FeMn Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- 241000408659 Darpa Species 0.000 description 1
- -1 FeB Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating By Spraying Or Casting (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of strong glass forming ability Fe-based amorphous alloy and the high-compactness amorphous alloy coating of resistance to long-term corrosion, belong to field of surface engineering technique, non-crystaline amorphous metal chemical formula is FeaCrbMocMxPdBeCfSig, M is at least one of Mn, Ni, W, 16≤b≤22,5≤c≤10,2≤x≤5,9≤d≤15,1≤e≤5,2≤f≤6,1≤g≤4, balance of Fe.AMORPHOUS ALLOY RIBBONS is prepared using single roller melt supercooled method, the powder of Fe-based amorphous alloy is obtained using ultrasonic gas atomization method.Using HVAF technology, the alloy powder is sprayed on carbon steel substrate surface and obtains iron base amorphous alloy coatings.The alloy material has completely amorphous state structure, high rigidity and excellent corrosion resistance；Powder body material has the amorphous degree of sphericity and superelevation higher；Coating has superelevation content of amorphous, ultralow porosity and excellent resistance to long-term corrosion performance.
Description
Technical field
The present invention relates to field of surface engineering technique, and in particular to a kind of strong glass forming ability Fe-based amorphous alloy and height
The consistency amorphous alloy coating of resistance to long-term corrosion.
Background technology
Amorphous alloy has numerous excellent properties due to its unique architectural characteristic, such as high rigidity, high-wearing feature, height
Elastic limit, excellent soft magnet performance and corrosion resistance etc..Wherein, one of performance of concern is most made to be high corrosion-resistant, this
Mainly have benefited from following two aspect：One be in amorphous alloy can solid solution exceed well over anti-corrosion group of balance crystal alloy solid solubility
Unit, it is easy to form the passivating film of stabilization and there is good passivation ability again；Two is that corrosion is typically free of in amorphous alloy is quick
Sense position, such as dislocation, crystal boundary and the equal crystal defect of crystal.The limit of bulk amorphous alloy size and intrinsic fragility in addition
System, amorphous coating is arisen at the historic moment.In numerous amorphous coating systems, iron base amorphous alloy coatings are most should
One of system with prospect；It is wherein foremost to be the institute under the support of advanced project research office (DARPA) of U.S. Department of Defense
The SAM series alloy compositions of exploitation, such as SAM2X5 and SAM1651.Current iron-based amorphous coating petrochemical industry, electric power, ocean and
The field successful Application such as nuclear industry shows broad prospect of application.
As it was previously stated, amorphous alloy generally has high corrosion-resistant, but the corrosion resistance of amorphous alloy coating then drops significantly
Low, the passive current density of usual coating generally increases an order of magnitude than corresponding fine and close non-crystaline amorphous metal.Its main cause
It is alloy by the coating that is obtained after the kinds of processes such as melting, powder processed and spraying, its structure and chemical uniformity are substantially reduced,
This inhomogeneities key factor is two aspects.Firstly, since the limitation of glass alloy Forming ability, coating is not usually complete
Amorphous structure, wherein containing various crystal phases.These crystal phases will increase coating with the corrosion potential difference of noncrystal substrate
Inhomogeneities, it is prone to micro- galvanic corrosion.Secondly, heat spraying method be generally acknowledge at present to prepare iron-based amorphous coating most preferable
Method, such as HVAF (HVOF or HVAF).Supersonic flame spraying method can be reduced largely in coating
These defects in hole and crack defect, but coating are still inevitable.Its main cause is except relevant with coating production
Outward, its substantially with the flowing spreading property and the close phase of intrinsic fragility of material of alloy melting or semi-molten state itself
Close.These performances can generally be reflected by simple hardness parameter.Thermal spraying empirical law according to metal coating can be with
Find out have compared with multiple crackses in obtained coating when the excessive high hardness of alloy, and more multiple crackses can be also produced during usage.
In corrosive environment, these crackles are interconnected causing corrosion medium osmosis to coating-substrate interface with porosity defects, are caused
Matrix heavy corrosion, ultimately results in corrosion protective coating failure.And the corrosion protective coating of marine environment military service component is directed to, it is special
When not being that pair wear extent of the component frequently contacted with coating has higher requirements, it is usually desirable to which the hardness of coating material should not be special
Height, and more focus on its corrosion resisting property.In sum, in some harsh usage environment, such as in chloride ion-containing medium, amorphous is applied
The defects such as crystal phase and hole, crackle in layer will substantially reduce the corrosion protection effect and service life of iron-based amorphous coating,
So as to limit extensive use of the iron-based amorphous coating in association area.Therefore, being developed by design of alloy has glass high
Glass Forming ability, the corrosion resistant alloy system of relatively low hardness have important application value.
The content of the invention
For above-mentioned weak point present in present technology, energy is formed it is an object of the invention to provide a kind of strong glass
Power Fe-based amorphous alloy and the high-compactness amorphous alloy coating of resistance to long-term corrosion, anti-corrosion Fe-based amorphous alloy prepared by the present invention are same
When there is glass forming ability high and relatively low hardness, using the alloy prepare alloy powder material spraying obtained in apply
Layer also has amorphous degree, ultrahigh relative density and the excellent resistance to long-term corrosion performance of superelevation.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of strong glass forming ability Fe-based amorphous alloy, it is characterised in that：The Fe-based amorphous alloy chemical expression is
FeaCrbMocMxPdBeCfSig, a, b, c, x, d, e, f and g are atomic percentage conc, and a+b+c+x+d+e+f+g=100；Wherein：
M be selected from Mn, Ni and W at least one element, 16≤b≤22,5≤c≤10,2≤x≤5,9≤d≤15,1≤e≤5,2≤
F≤6,1≤g≤4, balance of Fe.
In the Fe-based amorphous alloy chemical expression, each component preferred scope is：17≤b≤21,6≤c≤9,3≤x≤
5,10≤d≤14,2≤e≤4,3≤f≤5,2≤g≤3.
Fe, Mn, Ni element are used as alloy substrate in the present invention；Cr, Mo, W and Si element are added to raising corrosion resisting property.
By being found after lot of experiments, when Fe-based amorphous alloy is using as above chemical formula, the alloy has high
Glass forming ability and excellent corrosion resisting property, and relative to SAM2X5 alloys there is relatively low hardness, the powder of the alloy
Material and the obtained coating of spraying have the amorphous degree and consistency of superelevation, and excellent resistance to long-term corrosion performance：
The selection of glass formation element P, B, C and Si in non-crystaline amorphous metal of the present invention.Wherein, P, B, Si element and matrix Fe units
There is larger negative value enthalpy of mixing between element, be important glass formation element；Enthalpy of mixing between C element and Fe elements be on the occasion of,
But it is easily formed complex compound, such as Fe in crystallization process23(B,C,P)6Deng appropriate to add also beneficial to raising glass formation energy
Power.
P is content highest nonmetalloid in the present invention, is acted synergistically by with other elements, except that can improve
Outside cold liquid phase region stability, promotion amorphous formation, alloy fragility can also be reduced, fusing point and hardness is reduced.
Fe-based amorphous alloy of the present invention is ribbon or powder, ribbon Fe-based amorphous alloy (ferrum-based amorphous alloy strip)
Preparation process it is as follows：
(1) mother alloy ingot is prepared first, and preparation process is：With technical grade high-carbon FeCr, low-carbon (LC) FeCr, FeMo, FeW,
The intermediate alloys such as FeP, FeB, FeMn, high-purity N i and simple substance Si are raw material, according to the above-mentioned chemistry point of the Fe-based amorphous alloy
Minor carries out dispensing, and the raw material that will be obtained carries out melting in superhigh temperature smelting furnace, and mother alloy ingot is obtained after cooling；Using work
Industry level intermediate alloy can reduce the universal adaptability of volatilization, reduces cost and the raising present invention to raw material of raw material；
(2) sensing heating fusing fritter mother alloy ingot, then obtains Fe-based amorphous alloy using single roller melt supercooled method
Band.
Prepared ferrum-based amorphous alloy strip be completely amorphous state structure, thickness be 25~35 μm, width be 2.5~
3.5mm；Pitting resistance of the ferrum-based amorphous alloy strip in 3.5wt.% sodium chloride solutions is far above matrix material carbon steel, also
Better than 316L stainless steels.
Powder shaped Fe-based amorphous alloy (Fe-based amorphous alloy powder) is prepared from using ultrasonic gas atomization technique, its system
Standby process comprises the following steps：
(1) according to above-mentioned foundry alloy preparation method, mother alloy melt is cast to special shape formwork, mother is obtained after cooling
Alloy cast ingot；
(2) mother alloy ingot that step (1) is obtained is reheated using vacuum ultrasonic gas atomization device and melts and spray
Fog cooling, gas atomization process is carried out in argon gas atmosphere, and Fe-based amorphous alloy powder is obtained after cooling.
Step (2) gained Fe-based amorphous alloy powder screening is obtained into three kinds of particle size range powders：18~<53 μm, 53~<
95 μm and 95~180 μm；Wherein：Particle diameter is completely amorphous structure less than 95 μm of alloy powders；Granularity is 95~180 μm of alloy
There is no obvious crystal diffraction peak, essentially completely amorphous structure in Powder XRD pattern.
Present invention also offers a kind of strong glass forming ability iron base amorphous alloy coatings of resistance to long-term corrosion of matrix surface,
Matrix can be carbon steel, stainless steel or particular surroundings steel.The coating is using the method for HVAF HVAFs, by granularity
Scope 18~<53 μm of Fe-based amorphous alloy powder heating is melted and is sprayed into matrix surface and obtains；The HVAF supersonic speed
In flame spraying method, fuel gas is used pentane as, compressed air improves technique as combustion adjuvant using hydrogen and nitrogen
Flexibility.The process conditions of the HVAF supersonic flame spraying methods are：85~95psi of air pressure；Gaseous-pressure 75
~85psi；Propane flow：125~145SLPM；Hydrogen flowing quantity：30~40SLPM；Nitrogen flow：25~35SLPM；Powder feeding speed
Rate：5~8rpm；Spray distance：160~240mm.
Prepared iron base amorphous alloy coatings are essentially completely amorphous state structure, amorphous phase volume fraction >=95%；Apply
Layer has ultrahigh relative density, porosity≤0.5%；The B117 of resistance to ASTM salt spray tests are more than 3000 hours without rust spot.
Compared with existing Fe-based amorphous alloy, powder and coating, the present invention has the beneficial effect that：
(1) Fe-based amorphous alloy has Cr elements higher in the present invention, can make up coating mesopore and oxidation defect draws
The deficiency of Cr elements in the Cr depletion zone for rising, so that amorphous coating keeps corrosion resisting property higher；P element content high in alloy
Glass forming ability can be improved, fusing point is reduced, reduce hardness and is increased plasticity.
(2) ferrum-based amorphous alloy strip, powder and coating are respectively provided with the amorphous degree of superelevation in the present invention.For example, particle diameter is small
In 95 μm of alloy powders be completely amorphous structure；Only have tiny crystals in the XRD spectrum of the alloy powder that 95~180 μm of granularity to spread out
Penetrate peak, essentially amorphous structure.
(3) present invention in use industrial raw material master alloy melting, can effectively reduces cost and beneficial to engineering application.Profit
With amorphous degree >=95% of iron base amorphous alloy coatings obtained in the amorphous powdered alloy in the present invention, porosity≤0.5% is resistance to
ASTM B117 salt spray tests were more than 3000 hours.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of obtained non-crystaline amorphous metal powder in the embodiment of the present invention 1；In figure：(a) particle size range
18-53μm；95-180 μm of (b) particle size range；
Fig. 2 is obtained amorphous alloy coating stereoscan photograph in the embodiment of the present invention 1；In figure：(a) coating surface；
(b) coating cross sections；
Fig. 3 is obtained AMORPHOUS ALLOY RIBBONS, different grain size range alloys powder and amorphous coating in the embodiment of the present invention 1
X-ray diffraction (XRD) collection of illustrative plates；
Fig. 4 is obtained AMORPHOUS ALLOY RIBBONS, different grain size range alloys powder and amorphous coating in the embodiment of the present invention 1
Means of differential scanning calorimetry (DSC) curve；
Fig. 5 be SAM2X5 AMORPHOUS ALLOY RIBBONSs, the embodiment of the present invention 1 with and embodiment 2 in obtained AMORPHOUS ALLOY RIBBONS
Microhardness figure；
Fig. 6 be the embodiment of the present invention 1 in obtained AMORPHOUS ALLOY RIBBONS, corresponding amorphous alloy coating, plain steel,
The dynamic potential polarization curve of 316L stainless steels and SAM2X5 amorphous coatings in 3.5wt.%NaCl solution；
Fig. 7 be the amorphous alloy coating of the embodiment of the present invention 1 and SAM2X5 amorphous coatings according to ASTM B117 salt spray tests,
Photo during continuous spray test in 5wt.%NaCl solution；In figure：(a) SAM2X5 amorphous coatings；(b) embodiment 1
Amorphous alloy coating.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is further elaborated on the present invention, embodiment described below is intended to readily appreciate this
Invention, and do not play any restriction effect to it.In following embodiment, Fe-based amorphous alloy chemical expression is
FeaCrbMocMxPdBeCfSig, a, b, c, x, d, e, f and g are atomic percentage conc, and a+b+c+x+d+e+f+g=100.
Embodiment 1：
In the present embodiment, the chemical formula of Fe-based amorphous alloy is Fe50Cr18Mo7.5Ni3.5P12B3C3.5Si2.5.Prepare first
Foundry alloy：With the intermediate alloy such as technical grade high-carbon FeCr, low-carbon (LC) FeCr, FeMo, FeW, FeP, FeB, FeMn, high-purity N i and list
Matter Si is raw material, and after carrying out dispensing according to above-mentioned chemical formula, the raw material that will be obtained carries out melting in superhigh temperature smelting furnace, cooling
After obtain mother alloy ingot.Mother alloy ingot is cut into fritter, after polishing cleaning treatment, is obtained using single roller melt supercooled method
AMORPHOUS ALLOY RIBBONS.Prepared band is completely amorphous state structure after testing, and its thickness is about 35 μm, and width is about 3mm.
Fe-based amorphous alloy powder is prepared, is mainly included the following steps that：(1) method of smelting is matched according to above-mentioned foundry alloy,
Mother alloy melt is cast to special shape formwork, special shape mother alloy ingot is obtained after cooling；(2) by the mother alloy ingot
Fusing and misting cooling are reheated using vacuum ultrasonic gas atomization equipment in argon gas atmosphere, Fe-based amorphous alloy powder is obtained
Body；(3) powder of above-mentioned acquisition sieve and obtain three kinds of particle size range powder：18~<53 μm, 53~<95 μm and 95~
180μm。
The electron scanning micrograph of amorphous powdered alloy obtained above is as shown in figure 1, wherein Fig. 1 (a) granularities are
The powder of 18-53 μ ms, Fig. 1 (b) granularities are the powder of 95-180 μ ms.As can be seen that two kinds of powder of particle size range
It is respectively provided with sphericity higher, surface smoother；Powder does not have obvious contrast difference in back scattering photo, shows its composition
Than more uniform.
Choose the 18-53 μm of powder of particle size range, using HVAF (High Velocity Air Fuel,
HVAF) technology, alloy powder heating is melted and the prepared iron base amorphous alloy coatings model of carbon steel substrate is sprayed into.Spraying process
In, fuel gas is used pentane as, compressed air improves the flexibility of technique using hydrogen and nitrogen as combustion adjuvant.Make
For preferred, described spraying coating process condition is：Air pressure 90psi；Gaseous-pressure 80psi；Propane flow：135SLPM；Hydrogen
Flow：35SLPM；Nitrogen flow：30SLPM；Powder feeding rate：7rpm；Spray distance：210mm.
Surface topography and Cross Section Morphology using iron base amorphous alloy coatings obtained in the above method is as shown in Figure 2 respectively.
By Fig. 2 (a) it can be seen that unfused particle does not occur in coating surface, powder fusing is abundant under showing the process conditions；By Fig. 2
B the sectional view of () can be seen that between coating and matrix that boundary line does not clearly show that its preferable combination, about 500 μm of coating layer thickness,
There is no macrovoid in coating and consistency is higher, further by 10 stereoscan photographs of 1000 × multiplication factor, use
The porosity of the coating that image analytical method is calculated is 0.46%.
The XRD spectrum of amorphous ribbon obtained above, the amorphous powder of different grain size scope and amorphous coating such as Fig. 3 institutes
Show.As can be seen that there is no crystal peak in the corresponding collection of illustrative plates of alloy powder of amorphous ribbon, amorphous coating and particle diameter less than 95 μm,
Show that it is completely amorphous state structure；Only has tiny crystals diffraction in the XRD spectrum of the alloy powder that 95~180 μm of particle diameter
Peak, essentially amorphous structure.
DSC collection of illustrative plates such as Fig. 4 institutes of amorphous ribbon obtained above, the amorphous powder of different grain size scope and amorphous coating
Show.By the area of comparing calculation crystallization exothermic peak, it can be deduced that alloy powder of the particle diameter less than 95 μm is completely amorphous state knot
Structure；The content of amorphous of the alloy powder that 95~180 μm of particle size range is 96%, and the content of amorphous of amorphous coating is 98%.
The hardness of ferrum-based amorphous alloy strip obtained above is tested using microhardness testers, it is same to prepare SAM2X5 amorphous
Band is as a comparison；Load used is 0.3kg, 15 seconds action time, randomly selects 10 regions and measures, and test result is such as
Shown in Fig. 5.It can be seen that the average hardness of SAM2X5 alloys is 1270HV0.3, Fe-based amorphous alloy is average hard in the present embodiment
It is 1123HV to spend0.3, reduce 11.6%.
Ferrum-based amorphous alloy strip obtained above and corresponding amorphous coating short term corrosion are evaluated with electrochemical workstation
Can, Fig. 6 illustrates Fe-based amorphous band, corresponding amorphous coating, plain steel, 316L stainless steels, SAM2X5 amorphous coatings and exists
Dynamic potential polarization curve in 3.5wt.%NaCl solution.As can be seen from Figure, plain steel is not passivated, and has
Highest corrosion electric current density and minimum corrosion potential；Amorphous ribbon, amorphous coating and 316L stainless steels are passivated immediately, but
Stainless steel is 0.33V in current potentialSCEShi Fasheng spot corrosion, and there is no spot corrosion in amorphous ribbon and coating, passivation interval width exceedes
1000mV, shows its excellent corrosion-resistant ability；Amorphous ribbon in the present embodiment has minimum passive current density, entirely
The passive current density of the amorphous coating in passivation region in the present embodiment is respectively less than the passive current density of SAM2X5 amorphous coatings,
Show that it has excellent passivation ability.
For the amorphous coating in the present embodiment and SAM2X5 coatings, its is evaluated using ASTM B117 salt spray tests long-term
Corrosion behavior, experimental condition is continuously sprayed for 5wt.%NaCl solution, and result of the test is as shown in Figure 7.It can be seen that SAM2X5 is applied
Has there are multiple obvious rust stainings by surface after 1200 hours in layer, and amorphous coating is by table after 3096 hours in the present embodiment
Face occurs without rust staining, shows its excellent resistance to long-term corrosion performance.
Embodiment 2：
In the present embodiment, the chemical formula of Fe-based amorphous alloy is Fe50Cr18Mo7.5Mn2W1.5P12B3C3.5Si2.5, the iron-based is non-
The preparation method of raw material and fusion process, the preparation of amorphous ribbon, powder body material used by peritectic alloy master alloy melting with reality
The corresponding contents applied in example 1 are essentially identical, except that according to chemical formula Fe50Cr18Mo7.5Mn2W1.5P12B3C3.5Si2.5In
Atomic percent prepares foundry alloy raw material.
Amorphous ribbon thickness obtained above is about 30 μm, and width is about 3.5mm, through x-ray diffraction experiment analysis shows
Prepared band is completely amorphous state structure.
Same as Example 1, alloy powder sphericity obtained above is higher, with good mobility；The amorphous is closed
The X-ray diffractogram at bronze end shows that alloy powder of the particle diameter less than 95 μm is completely amorphous state structure；95~150 μm of particle diameter
Only have a small amount of tiny crystals diffraction maximum in the XRD spectrum of alloy powder, alloy powder can be obtained with reference to DSC crystallization enthalpy result of calculations
Content of amorphous is 98%.
It is same as Example 1, the 18-53 μm of powder of particle size range is still chosen for HVAF, spraying coating process
Parameter is as follows：Air pressure 85psi；Gaseous-pressure 75psi；Propane flow：130SLPM；Hydrogen flowing quantity：35SLPM；Nitrogen stream
Amount：30SLPM；Powder feeding rate：7rpm；Spray distance：200mm.Prepared coating surface fusing is abundant, and coating layer thickness is about
500 μm, using coating cross sections SEM photograph, the porosity for calculating coating using image analytical method is 0.5%.With reference to XRD and DSC
The content of amorphous that test result can calculate amorphous coating is 95%.
Method same as Example 1 tests the microhardness of the Fe-based amorphous alloy, test result as shown in figure 5, should
The average hardness of Fe-based amorphous alloy is 1156HV0.3, compared to the average hardness value 1270HV of SAM2X5 alloys0.3Reduce
8.98%.
Method same as Example 1 has carried out electro-chemical test and salt spray test, as a result shows obtained non-crystal bar
Band and coating are respectively provided with excellent passivation ability, and passive current density is less than SAM2X5 coatings, show that it has than 316L stainless steel
There is more excellent pitting resistance；ASTM B117 salt spray tests also indicate that obtained amorphous coating is molten in 5wt.% sodium chloride
Under the continuous spray condition of liquid, coating surface does not have rust spot after 3000 hours, shows its excellent resistance to long-term corrosion performance.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of strong glass forming ability Fe-based amorphous alloy, it is characterised in that：The Fe-based amorphous alloy chemical expression is
FeaCrbMocMxPdBeCfSig, a, b, c, x, d, e, f and g are atomic percentage conc, and a+b+c+x+d+e+f+g=100；Wherein：
M be selected from Mn, Ni and W at least one element, 16≤b≤22,5≤c≤10,2≤x≤5,9≤d≤15,1≤e≤5,2≤
F≤6,1≤g≤4, balance of Fe.
2. strong glass forming ability Fe-based amorphous alloy according to claim 1, it is characterised in that：The Fe-based amorphous alloy
In chemical expression, 17≤b≤21,6≤c≤9,3≤x≤5,10≤d≤14,2≤e≤4,3≤f≤5,2≤g≤3.
3. strong glass forming ability Fe-based amorphous alloy according to claim 1, it is characterised in that：The Fe-based amorphous conjunction
Gold be ribbon or powder, wherein：Ribbon Fe-based amorphous alloy is prepared from using single roller melt supercooled method, Fe-based amorphous conjunction
Bronze body is prepared from using ultrasonic gas atomization technique.
4. strong glass forming ability Fe-based amorphous alloy according to claim 3, it is characterised in that：The ribbon iron-based
Non-crystaline amorphous metal is completely amorphous state structure, and thickness is 25~35 μm, and width is about 2.5~3.5mm；Ribbon Fe-based amorphous alloy
Pitting resistance in 3.5wt.% sodium chloride solutions is higher than matrix material carbon steel, also better than 316L stainless steels.
5. strong glass forming ability Fe-based amorphous alloy according to claim 3, it is characterised in that：The Fe-based amorphous conjunction
The preparation process of bronze body comprises the following steps：
(1) raw material proportioning is carried out according to the chemical expression of Fe-based amorphous alloy, melting is carried out in high temperature induction furnace and is cast
Into formwork, mother alloy ingot is obtained after cooling；
(2) mother alloy ingot for obtaining step (1) reheats fusing and misting cooling, gas using ultrasonic gas atomization device
Body atomization process is carried out in argon gas atmosphere, and Fe-based amorphous alloy powder is obtained after cooling.
6. using the strong glass forming ability Fe-based amorphous alloy described in claim 5, it is characterised in that：Will be described Fe-based amorphous
Alloy powder screening obtains three kinds of particle size range powders：18~<53 μm, 53~<95 μm and 95~180 μm；Wherein：Particle diameter is less than
95 μm of alloy powders are completely amorphous structure；Granularity is do not have obvious crystal diffraction in 95~180 μm of alloy powder XRD spectrum
Peak, essentially completely amorphous structure.
7. the high-compactness amorphous alloy coating of resistance to long-term corrosion for being prepared using the Fe-based amorphous alloy described in claim 3, its
It is characterised by：The preparation of the amorphous alloy coating is the method using HVAF HVAFs, by particle size range 18~<53
μm Fe-based amorphous alloy powder heating melt and spray to substrate surface and obtain；The HVAF supersonic flame spraying methods
In, fuel gas is used pentane as, compressed air improves the flexibility of technique using hydrogen and nitrogen as combustion adjuvant.
8. using the high-compactness amorphous alloy coating of resistance to long-term corrosion described in claim 7, it is characterised in that：The HVAF surpasses
The process conditions of velocity of sound flame spraying method are：85~95psi of air pressure；75~85psi of gaseous-pressure；Propane flow：125
~145SLPM；Hydrogen flowing quantity：30~40SLPM；Nitrogen flow：25~35SLPM；Powder feeding rate：5~8rpm；Spray distance：
160~240mm.
9. using the high-compactness amorphous alloy coating of resistance to long-term corrosion described in claim 7, it is characterised in that：The amorphous is closed
The substrate of gold plating is carbon steel, stainless steel or particular surroundings steel.
10. using the high-compactness amorphous alloy coating of resistance to long-term corrosion described in claim 7, it is characterised in that：The amorphous
Amorphous phase volume fraction >=95% in alloy coat；Coating porosity≤0.5%；The B117 of resistance to ASTM salt spray tests are more than 3000
Hour, coating surface was without rust spot.
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