CN102534435A - Iron-based amorphous alloy powder, iron-based amorphous alloy coating and preparation method thereof - Google Patents
Iron-based amorphous alloy powder, iron-based amorphous alloy coating and preparation method thereof Download PDFInfo
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- CN102534435A CN102534435A CN2010106130833A CN201010613083A CN102534435A CN 102534435 A CN102534435 A CN 102534435A CN 2010106130833 A CN2010106130833 A CN 2010106130833A CN 201010613083 A CN201010613083 A CN 201010613083A CN 102534435 A CN102534435 A CN 102534435A
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Abstract
The invention discloses iron-based amorphous alloy powder capable of forming an amorphous alloy coating, and a method for preparing an amorphous coating. The amorphous alloy powder is taken as a raw material, and a complete amorphous coating is prepared by a cold spray method. The alloy powder mainly comprises Fe, Cr and Mo, can contain one or more of Ni, Co, Mn, Si, Re, Al, Cu, Nb, Zr, Ti, C, B and other elements, wherein Fe, Cr and Mo account for over 70 atomic percent of the alloy. The component has a wide supercooled liquid region and high amorphous forming capacity, amorphous powder can be obtained by an atomization powdering technology. In the process of preparing the amorphous alloy coating by the cold spray method, an inert gas such as nitrogen, helium and the like or a mixed gas of the nitrogen and helium is taken as a powder feeding gas and a powder accelerating gas, the temperature T of the inert gas is less than 700DEG C, and the powder feeding pressure P is 1-6MPa. The coating has a great application prospect in the fields such as wear resistance, corrosion resistance, radiation protection and the like.
Description
Technical field
The present invention relates to a kind of Fe-based amorphous alloy composition with strong amorphous formation ability; And the technological method for preparing this kind amorphous powdered alloy and amorphous coating; To promote through engineering approaches and even the large-scale application of Fe-based amorphous alloy on fields, particularly case material such as boats and ships, storage vessel such as wear-resisting, anti-corrosion and radioprotective.
Background technology
Non-crystaline amorphous metal is claimed metallic glass again, is a kind of metastable new metallic material; Have short range order, unordered constitutional features and the excellent properties such as HS, high firmness, high elastic coefficient, high abrasion and erosion resistance of long-range, also have very excellent magnetic performance in some non-crystaline amorphous metal.As a kind of new-type functional material and engineering materials, non-crystaline amorphous metal has broad application prospects in fields such as aerospace, military project, automobile, electronics, instrument, sports equipment, medical devices.Since the sixties in 20th century, the exploitation of amorphous alloy material is the focus of material educational circles research with using always.
Fe-based amorphous alloy has performances such as excellent physics, chemistry, mechanics as one type of very important amorphous alloy material, more and more receives people's attention.Although preparation of bulk amorphous alloys at present and application also are limited to laboratory and extremely indivedual occasion; And non-crystaline amorphous metal is as functional materials, with the application of low dimension shape materials such as strip, filament, powder more and more widely.For example, the Fe-based amorphous alloy band has been widely used in magnetic field of materials such as X-former, RF as soft magnetic materials.The research of Fe-based amorphous alloy coating and application have also had many breakthroughs: scientists utilizes HVAF technology and plasma spraying technology to prepare the Fe-based amorphous alloy coating; And their performance carried out comprehensive research; Obtained a large amount of achievements, for new field has been opened up in the application of non-crystaline amorphous metal.
Yet traditional hot-spraying techniques is to be heated to fusion or semi-melting state and high-velocity jet to certain solid material to matrix surface, to form the rete with specified property, to reach the process for treating surface to matrix surface upgrading purpose.So under many circumstances, thermospray can cause decomposition and the volatilization and the oxidation of phase transformation, part element.The above-mentioned shortcoming of thermospray is unfavorable for being used for preparing amorphous alloy coating very much.So people manage to explore technology and the method that is applicable to the thermally sensitive amorphous alloy coating of preparation.Patent " contain the method that Fe-Si-B is an amorphous phase coating a kind of on alloy matrix aluminum, the preparation " (application number: 200910084510.0) protected employing heavy impulse current direct heating to have the blast sheet of amorphous component, utilized electric heating and electrical explosion to prepare the method for amorphous coating.This method can solve the technological difficulties that thermospray is difficult for preparation amorphous alloy coating on alloy matrix aluminum.Patent " a kind of preparation method of Ni-based complete amorphous alloy coating of high anti-corrosion " (application number: 200510046340.9) protected a kind of kinetic metallization technology.Because crystallization and oxidation can not take place in amorphous powdered alloy in this method, thereby can obtain complete amorphous alloy coating; This coating shows excellent corrosion resisting property.But the gaseous tension in the kinetic metallization technology is low pressure (gas velocity is limited in about velocity of sound), limited should technology practical application.
Up to the present, comprise all acquisition research and practical applications in a big way of amorphous alloy coating technology of preparing of aforesaid method.And the cold spray technique that development in recent years is got up can be realized the preparation of high-performance metal coating better on industrialized level.Cold spraying CS (Cold Spray); Claim freezing air kinetics spraying method CGDSM (Cold Gas Dynamic Spray Method) or CGDS again; CGSM; Its principle is to utilize high pressure gas to pass through the convergent-divergent pipe to produce supersonic speed and flow, and powder particle is from axially sending into high velocity air and under solid-state fully, clashing into matrix through quickening the back; Thereby powder particle is deposited on through bigger plastic flow distortion and forms dense coating on the matrix surface.In order to increase the speed of air-flow, after can also will speed up the gas preheating, the movement velocity that further improves particle sends into spray gun.When spraying, spraying particle is so that (500～1200m/s) clash into matrix surfaces, and not fusing of particle keeps solid state in whole process, and particle pure viscous deformation polymerization takes place forms coating at a high speed.Therefore, cold spray technique is specially adapted to thermally sensitive nanocrystalline, non-crystaline amorphous metal; To pure metal or alloys such as the Cu of oxidation-sensitive, Ti; Cermet material to the phase sensitize.In addition, cold spray technique also has following two advantages: during 1. owing to the high-velocity particles collision matrix or coatingsurface are had intensive shot-peening effect, so generally be in compressive stress state in the coating.This helps the deposition than thick layer, and thickness can reach centimetre-sized; 2. because powder does not experience the variation that weave construction does not take place tangible thermal process basically, not sedimentary particle can be recycled.
In recent years, cold spray technique has all obtained very fast development in Russia, the U.S., Germany, Canada, Australia, Japan etc.
Summary of the invention
The object of the present invention is to provide a kind of Fe-based amorphous alloy powder and Fe-based amorphous alloy coating and preparation method thereof.Fe-based amorphous alloy powder of the present invention has the Fe-based amorphous alloy composition of strong amorphous formation ability, is raw material with the Fe-based amorphous alloy powder, adopts cold spray technique to make amorphous alloy coating.Fe-based amorphous alloy powder of the present invention and Fe-based amorphous alloy coating and preparation method thereof can promote through engineering approaches and even the large-scale application of Fe-based amorphous alloy on fields, particularly case material such as boats and ships, storage vessel such as wear-resisting, anti-corrosion and radioprotective.Above-mentioned preparation method is with a wide range of applications, for the preparation of amorphous alloy coating provides a kind of feasible method and technology.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
A kind of Fe-based amorphous alloy powder, the Fe-based amorphous alloy of this Fe-based amorphous alloy powder chemistry table answer formula for (Fe, Cr, Mo)
xA
(100%-x), wherein, 70%≤x＜100%; A is one or more in Ni, Co, Mn, Si, Re, Al, Cu, Nb, Zr, Ti, C and the B element.
Wherein, " % " is that " at.% " refers to atomic percent in the formula.Fe, Cr, three kinds of atoms of elements percentage compositions of Mo account for more than 70% of alloy.
In Fe-based amorphous alloy powder of the present invention, described Fe-based amorphous alloy powder be complete non-crystalline state powder or in described Fe-based amorphous alloy powder the percent by volume of crystallization powder less than 20%.
In Fe-based amorphous alloy powder of the present invention, described Fe-based amorphous alloy powder is spherical, subsphaeroidal or type sphere.
In Fe-based amorphous alloy powder of the present invention, the granularity of described Fe-based amorphous alloy powder＜50 μ m.
A kind of is raw material with Fe-based amorphous alloy powder of the present invention, adopts cold spray-coating method to make the Fe-based amorphous alloy coating.
A kind of preparation method of Fe-based amorphous alloy coating; With Fe-based amorphous alloy powder of the present invention is raw material, adopts the cold spray-coating method preparation, prepares in the amorphous alloy coating process at said cold spray-coating method; With the gas and gas that powdered alloy quickened of rare gas element as the conveying powdered alloy; The temperature of rare gas element is T, and 50 ℃＜T＜700 ℃, the pressure P of rare gas element is 1～6MPa.
In the preparation method of Fe-based amorphous alloy coating of the present invention, said rare gas element is nitrogen, helium or their mixed gas.
The present invention adopts the Fe-based amorphous alloy composition with strong amorphous formation ability; And adopt the aerosolization technology to obtain amorphous powdered alloy; The cold spray technique that utilizes recent development to rise, preparation have excellent wear-resisting, corrosion resisting property, radiation-resistant Fe-based amorphous alloy coating.Because crystallization and oxidation do not take place in cold spray process amorphous powdered alloy, the non-crystalline state of powder is able to keep.
Advantage of the present invention is:
Fe-based amorphous alloy powder of the present invention has the Fe-based amorphous alloy composition of very wide supercooling liquid phase region and very strong amorphous formation ability; The present invention is to be raw material with the Fe-based amorphous alloy powder; Adopt cold spray-coating method to make amorphous alloy coating; Cold spray-coating method is a kind of feasible potential technology for preparing the very strong amorphous alloy coating of heat sensitivity; Fe-based amorphous alloy coating of the present invention and preparation method thereof will promote through engineering approaches and even the large-scale industrial application of amorphous alloy coating on fields, particularly case material such as boats and ships, storage vessel such as wear-resisting, anti-corrosion and radioprotective.
Description of drawings:
Fig. 1 is the X-ray diffraction result of Fe-Cr-Mo-X (X is one or more in the elements such as Ni, Co, Mn, Si, Re, Al, Cu, Nb, Zr, Ti, C, the B) amorphous powdered alloy of aerosolization preparation;
Fig. 2 is the X-ray diffraction result of the Fe-Cr-Mo-X amorphous alloy coating of cold spraying preparation.
Embodiment:
Fe-based amorphous alloy of the present invention (Fe-Cr-Mo-X) powder staple is: Fe, Cr, Mo; Can contain in the elements such as Ni, Co, Mn, Si, Re, Al, Cu, Nb, Zr, Ti, C, B one or more; Wherein, Fe, Cr, three kinds of atoms of elements percentage compositions of Mo account for more than 70% of alloy.This composition has very wide supercooling liquid phase region and very strong amorphous formation ability.
Fe-based amorphous alloy powder of the present invention powder by gas-atomization technology capable of using obtains amorphous powder.Powder is spherical, subsphaeroidal or type sphere; And the powdered alloy of aerosolization preparation carried out the choosing branch of granularity and shape, the acquisition amorphous powdered alloy is that complete non-crystalline state or crystallization volume(tric)fraction are less than 20%;
Spraying of the present invention is with the granularity＜50 μ m of Fe-based amorphous alloy powder.Fe-based amorphous alloy coating of the present invention adopts the cold spray-coating method preparation.
Said cold spray-coating method prepares in the amorphous alloy coating process, with rare gas elementes such as nitrogen, helium or their mixed gas as powder feeding gas and powder accelerating gas.
Said cold spray-coating method prepares in the amorphous alloy coating process, the temperature T of rare gas element＜700 ℃, and the powder feeding pressure P is 1～6MPa.
Embodiment 1
The design alloying constituent is Fe
49.5Cr
15Mo
14Y
0.5C
15B
6(at.%), adopt vacuum induction melting to prepare mother alloy; Adopt ultra-high voltage inert gas atomizer technology preparation amorphous powdered alloy.The result is as shown in Figure 1 for its X-ray diffraction.Show that powdered alloy is complete non-crystalline state.
Above-mentioned amorphous powdered alloy is chosen the spray powders granularity and is＜45 μ m through screening.As powder feeding gas and powder accelerating gas, temperature is 300 ℃ with nitrogen, and nitrogen pressure is 5MPa.The X-ray diffraction result of coating is as shown in Figure 2.Show that coating is complete non-crystalline state coating.
Embodiment 2
The design alloying constituent is Fe
50Cr
17.5Mo
7Si
3Mn
2W
2B
15C
3.5(at.%), adopt vacuum induction melting to prepare mother alloy; Adopt ultra-high voltage inert gas atomizer technology preparation amorphous powdered alloy.The X-ray diffraction result shows that powdered alloy is complete non-crystalline state.
Above-mentioned amorphous powdered alloy is chosen the spray powders granularity and is＜50 μ m through screening.As powder feeding gas and powder accelerating gas, temperature is 500 ℃ with helium, and nitrogen pressure is 2MPa.The X-ray diffraction result of coating shows that coating is complete non-crystalline state coating.
Claims (7)
1. Fe-based amorphous alloy powder is characterized in that: the Fe-based amorphous alloy chemistry table of this Fe-based amorphous alloy powder answer formula for (Fe, Cr, Mo)
xA
(100%-x), wherein, 70%≤x＜100%; A is one or more in Ni, Co, Mn, Si, Re, Al, Cu, Nb, Zr, Ti, C and the B element.
2. Fe-based amorphous alloy powder according to claim 1 is characterized in that, described Fe-based amorphous alloy powder be complete non-crystalline state powder or in described Fe-based amorphous alloy powder the percent by volume of crystallization powder less than 20%.
3. Fe-based amorphous alloy powder according to claim 1 is characterized in that, described Fe-based amorphous alloy powder is spherical, subsphaeroidal or type sphere.
4. Fe-based amorphous alloy powder according to claim 1 is characterized in that, the granularity of described Fe-based amorphous alloy powder＜50 μ m.
5. one kind is raw material with the described Fe-based amorphous alloy powder of claim 1, adopts cold spray-coating method to make the Fe-based amorphous alloy coating.
6. the preparation method of a Fe-based amorphous alloy coating; It is characterized in that: with the described Fe-based amorphous alloy powder of claim 1 is raw material, adopts the cold spray-coating method preparation, prepares in the amorphous alloy coating process at said cold spray-coating method; With the gas and gas that powdered alloy quickened of rare gas element as the conveying powdered alloy; The temperature of rare gas element is T, and 50 ℃＜T＜700 ℃, the pressure P of rare gas element is 1～6MPa.
7. according to the preparation method of the described Fe-based amorphous alloy coating of claim 6, it is characterized in that: said rare gas element is nitrogen, helium or their mixed gas.
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