CN101492795A - Iron based amorphous nanocrystalline composite coating - Google Patents
Iron based amorphous nanocrystalline composite coating Download PDFInfo
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- CN101492795A CN101492795A CNA2008100005531A CN200810000553A CN101492795A CN 101492795 A CN101492795 A CN 101492795A CN A2008100005531 A CNA2008100005531 A CN A2008100005531A CN 200810000553 A CN200810000553 A CN 200810000553A CN 101492795 A CN101492795 A CN 101492795A
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Abstract
The invention relates to a Fe-based amorphous nanocrystalline coating, the composition of the coating is expressed by atomic ratio as follows: Fe100-a-b-c-d-eNiaCrbPcTdDe, wherein, a is 0.5-8, b is 5-26, c is 3-15, d is 8-20 and e is 0-8; T is one or more of B, C and Si, and D is five or less of Y, V, Zr, Mo, Nb, Cu, Al, Ga, Sn, W and Mn. The coating can be hot spray coating, electric arc spray coating or plasma spray coating.
Description
Technical field
The invention belongs to the spray-on coating field.More specifically, the present invention relates to a kind of highly corrosion-proof abrasion-proof iron matrix amorphous nanocrystalline compound coating.
Background technology
The main failure forms of corrosion and wear metal part, cause great loss to national economy every year.For improving the reliability of part, prolong its work-ing life, the researchist develops constantly that material and technology give that part is high temperature resistant, protection against corrosion, performance such as wear-resistant, takes into account economy simultaneously.The principal feature of amorphous alloy is the arrangement that the three-dimensional space of atom is the topological disorder shape, does not have defectives such as crystal boundary and stacking fault to exist on the structure, its mainly with metallic bond as its constitutional features, do not have long-range order.This structures shape of amorphous alloy it have high hardness, intensity and excellent wear resistant corrosion resistant, be a kind of ideal corrosion-proof wear material.Nano material generally is meant the material that the particle of size between 1～100nm formed, and is that a kind of typical Jie sees system, has surface effects, small-size effect and macro quanta tunnel effect.The character of its optics, calorifics, electricity, magnetics, mechanics and chemical aspect and bulk crystalline state object have a great difference, demonstrate excellent performance.In the reality, for large block amorphous, nanocrystalline, prepare amorphous, the easier realization of nanocrystalline coating with heat spraying method.A lot of people have launched research in this respect, and coatings prepared or amorphous coating, or amorphous nanocrystalline composite coating, the excellent properties of this coating can satisfy the high request of wear resistant corrosion resistant field to material.
In U.S. Pat 6258185, people such as Daniel J.Branagand provide a kind of preparation method of amorphous nanocrystalline coating.At first, the material melts that will contain the Fe based component of multiple element, adopt technology such as aerosolization or centrifugal atomizing that the melt atomizing is prepared into amorphous powder, this amorphous powder is adopted technology such as plasma spraying, HVOF (High Velocity Oxygen Fuel) form amorphous coating, form the nanocrystalline structure coating at 600 ℃ to thermal treatment coating crystallization between the fusing point at last at matrix surface.Compare amorphous or traditional crystalline coatings, this coating has high strength, high rigidity and good toughness.
J.Thermal Spray Technology, 1999,8 (3): the 399-404 report, Mccartney D.J. sprays two kinds of Ni-Cr-Mo-B powdered alloys with supersonic flame spraying method, prepares the amorphous coating of two kinds of alloys, has good solidity to corrosion.
Chinese patent CN200610089515.9 has reported a kind of " electrical arc spraying method for preparing contains the powder cored filament material that the CrB amorphous coating is used ", and its powder core composition quality percentage composition is: boron chromium: 60～80%; Cr
3C
2: 5～20%; WC:5～10%; Surplus is Fe.Coating with this material preparation contains a large amount of amorphous, and coating structure is even, hardness is high, HV
0.1＞1190; Wear resisting property is good.
In a word, amorphous, nanocrystalline coating are causing more people's concern and research.This coating has characteristics such as preparation technology is simple, the cycle short, easy popularization, and application prospect is considerable.In order to obtain amorphous nanocrystalline coating, coated material should have certain amorphous formation ability.At present, the amorphous nanocrystalline coating material mainly concentrates on the material that amorphous formation ability is strong, alloy content is high, so cause the cost height, application is restricted.
Summary of the invention
The iron base heat spray amorphous nanocrystalline coating that the purpose of this invention is to provide a kind of corrosion-proof wear.Another object of the present invention provides a kind of coated material that has higher amorphous nano-crystalline to form ability.A further object of the present invention provides a kind of with low cost, simple amorphous nanocrystalline coating of preparation technology
To achieve these goals, the invention provides following technical scheme:
A kind of iron-based amorphous nanometer crystalline coat, the composition of this coating represents to satisfy following formula with atomic ratio:
Fe
100-a-b-c-d-eNi
aCr
bP
cT
dD
e，
Wherein, a is 0.5-8, and b is 5-26, and c is 3-15, and d is that 8-20 and e are 0-8; T is selected among B, C and the Si one or more, and D is selected among Y, V, Zr, Mo, Nb, Cu, Al, Ga, Sn, W and the Mn five kinds or still less.
In an embodiment of the invention, described coating is a hot spray coating.
In yet another embodiment of the present invention, described coating is an arc spraying coating.
In another embodiment of the present invention, described coating is a plasma spraying coating.
Description of drawings
Fig. 1 is the appearance photo of coating of the present invention
Fig. 2 is the X ray diffracting spectrum of coating of the present invention
Fig. 3 is the TEM photo of coating of the present invention
Fig. 4 is the anodic polarization curves of coating of the present invention
Embodiment
The invention provides a kind of iron-based amorphous nanometer crystalline coat, the composition of this coating represents to satisfy following formula with atomic ratio:
Fe
100-a-b-c-d-eNi
aCr
bP
cT
dD
e，
Wherein, a is 0.5-8, and b is 5-26, and c is 3-15, and d is that 8-20 and e are 0-8; T is selected among B, C and the Si one or more, and D is selected among Y, V, Zr, Mo, Nb, Cu, Al, Ga, Sn, W and the Mn five kinds or still less.
The invention further relates to a kind of iron-based amorphous nanometer crystalline coat, the composition of this coating represents to satisfy following formula with atomic ratio:
Fe
100-a-b-c-d-eNi
aCr
bP
cT
dD
e，
Wherein, a is 0.5-8, and b is 5-26, and c is 3-15, and d is that 8-20 and e are 0-8; T is selected from two or three among B, C and the Si, and D is selected among Y, V, Zr, Mo, Nb, Cu, Al, Ga, Sn, W and the Mn five kinds or still less.
In above-mentioned iron-based amorphous nanometer crystalline coat, can also contain the impurity that the total amount weight percent is no more than 0.5 weight %.Typical impurity for example comprises O, Pb, Zn, Ca, Cd, S and Mg etc.Enumerate some preferred implementations of above-mentioned iron-based amorphous nanometer crystalline coat involved in the present invention below.
In a preferred implementation, a is 0.5-6.
In a preferred implementation, b is 7-23, is preferably 9-21.
One preferred embodiment in, c is 4-14, is preferably 4-13.
One preferred embodiment in, d is 9-18, is preferably 10-18.
One preferred embodiment in, e is 0-7, is preferably 0-5.
In the material of iron-based amorphous nanometer crystalline coat of the present invention was formed, the main effect of B and Si was: by B, Si and Fe effect, significantly reduce alloy melting point, enlarge the solid-liquid phase line temperature province, improve the self-fluxing nature of alloy.Thus, can improve the amorphous formation ability of coated material.
P adds element for increasing the effective metalloid of alloy corrosion stability, and Cr adds element for improving effective second metal of corrosion stability in the amorphous alloy.Therefore, the common adding of P and Cr can impel the rapid formation of material passive film in corrosive environment, improves the Corrosion Protection of coated material.
The adding of other alloying element C, Y, V, Zr, Mo, Nb, Cu, Al, Ga, W, Mn, Ni and Sn etc. has improved the randomness of ferrous alloy system, so helps improving the formation ability of amorphous nano-crystalline.
In a specific embodiment of the present invention, coating of the present invention is a hot spray coating.In the preparation technology of this hot spray coating, employed thermal spraying material is iron base heat spray medicine core-wire material or iron base heat spray powder.
Described iron base heat spray medicine core-wire material is made up of coating and medicine core, and wherein coating has component X 1, and the medicine core has component X 2, and total composition X of coating and medicine core is in the mentioned component scope.The mixture that the medicine core can be made up of pure substance powder or alloy powder, this mixed thing has component X 2; The medicine core can also be the powder that is become by refabrication after the mixture melting with certain ingredients, and this powder has component X 2, and this powder cored filament material also can be used as resurfacing welding material.
Described iron base heat spray medicine core-wire material preparation method can adopt the method for prior art, for example can be by the method that may further comprise the steps:
1) steel band that will have an X1 composition rolls into the U type, adds the powder with X2 composition again in U type groove, and total composition X of X1 and X2 is in composition range of the present invention;
2) U type groove is healed up, the powder core wraps in wherein, through shaping, drawing tube reducing, obtains required silk material at last.
Described iron base heat spray powder can for example obtain with the following methods: directly be mixed with described metal-powder with pure metal powder or powdered alloy; Pure metal or alloy are made into required composition with powder or bulk, are atomized into powder after the fusing.The mode of atomizing can adopt but be not limited to water atomization or aerosolization; Pure metal or alloy are made into required composition with powder or bulk, and the fusing after coagulation adopts physical method to prepare powder.The method that the aforesaid method of preparation metal-powder is well known to those skilled in the art.Certainly, those skilled in the art also can adopt other method to obtain described iron base heat spray powder.
In yet another embodiment of the present invention, coating of the present invention is an arc spraying coating.For example, the preparation method who adopts arc spraying technology adopts twin wire arc spray equipment to spray, quicken to be deposited on the matrix with utilizing pressurized air to be atomized into drop after the fusing of medicine core-wire material, utilize the quick cooling effect of matrix directly to form amorphous nanocrystalline coating.Described preparation technology's concrete parameter can for, for example: arc voltage 30～34V, working current 190～230A, atomization pressure 0.6～0.8MPa, spray distance 150～200mm.Because electric arc spraying process is a spraying coating process well known in the prior art, therefore above-mentioned processing parameter only is exemplary.Those skilled in the art can select suitable processing parameter according to the particular case of required coating
In another embodiment of the present invention, coating of the present invention is a plasma spraying coating.For example, adopt the preparation method of plasma spraying technology to adopt common air plasma spraying method.The concrete parameter of spraying coating process can for, for example: arc voltage 50～80V, flame current 400～600A, main gas (Ar gas) 50～100L/min, secondary gas (H
2Gas) 25～50L/min, powder feed rate 20～100g/min, spray distance 50～150mm.Because plasma spray coating process is a spraying coating process well known in the prior art, therefore above-mentioned processing parameter only is exemplary.Those skilled in the art can select suitable processing parameter according to the particular case of required coating
In addition, coating related among the present invention also can be used other heat spraying method, for example flame plating preparation.The processing method of flame plating also is well-known to those skilled in the art.
In order to improve the binding ability of matrix and coating, and make full use of the quick cooling effect of matrix, can optionally carry out greasy dirt and the oxide compound that matrix surface is removed in pre-treatment before the spraying, increase roughness matrix.The method that is adopted for example comprises common pretreatment process, as cleaning, sandblast, wire drawing etc.Described pretreatment process all is the known methods of those skilled in the art, and those skilled in the art also can adopt other method that matrix is carried out pre-treatment as required.And, neither necessary step to the pre-treatment of matrix.
Amorphous nanocrystalline coating of the present invention can prepare easily by for example method recited above.As shown in Figure 2, the main body of the XRD of coating is the diffuse scattering peak of a broadening, illustrates that coating of the present invention is mainly non-crystal structure.In addition, the top of XRD figure spectrum is more sharp-pointed diffraction peak, illustrates that there is the crystallization phase in coating of the present invention.What in conjunction with sem analysis as can be known, the crystallization in the coating was a grain-size less than 100nm mutually is nanocrystalline.Hence one can see that, and coating of the present invention is an amorphous nanocrystalline composite coating.
Through measuring, the hardness of coating of the present invention is at 800～1200HV
0.1In the scope, the frictional coefficient between coating and the 45# steel column pin is 0.17.And coating wt does not lose because of friction, illustrates that coating has the advantages of good abrasion performance.The electrokinetic potential anodic polarization curves of coating of the present invention in 3.5 quality %NaCl solution, corrosion potential be-0.49V, has tangible passivation region, and passivation current density is 7.9 * 10
-3A/cm
2, as seen this coating has good corrosion resistance.Hence one can see that, and coating of the present invention has excellent corrosion-proof wear performance.
So in conjunction with above analysis as can be known, coating of the present invention is the nanocrystalline compound coating of amorphous.This coating has high rigidity, wear-resistant, corrosion resistant performance.Simultaneously, of the present invention the cost of material is low, has characteristics such as cost is low, convenient, the easy popularization of enforcement in conjunction with coating production.
Embodiment
In the present embodiment, adopt twin wire arc spray process and plasma spraying method to prepare amorphous nanocrystalline coating of the present invention, the composition of coating is as shown in table 1.
Concrete, when adopting twin wire arc spray to prepare coating, mentioned component is prepared the patent medicine core-wire material.Wherein, coating is the FeCr16 steel band.According to forming shown in the table 1, the medicine core is the uniform mixture that is selected from the powder constituent in Fe powder, Cr powder, Ni powder, Si powder, Cu powder, Mo powder, V powder, Zr powder, Y powder, Ga powder, Al powder, Sn powder, WC powder, Fe-B powder, Fe-Mn powder, Fe-P powder and the Fe-Nb powder, powder size is 60～200 orders, and the integral body composition of the powder cored filament material that obtains satisfies the composition shown in the above-mentioned table 1.Adopt electric arc spraying to prepare coating on the Q235 steel plate, spraying parameter is: arc voltage 34V, the about 200A of working current, atomization pressure 0.7MPa, spray distance 200mm.
When adopting plasma spraying method to prepare coating, according to forming shown in the table 1, be made into raw material with being selected from the pure metal of industrial usefulness of Fe, Cr, Ni, Si, Cu, Mo, Al, V, Zr, Y, Ga, Sn and WC and the alloy that is selected from the industrial usefulness of Fe-Mn, Fe-B, Fe-P and Fe-Nb, be atomized into metal-powder after the melting, total composition of metal-powder satisfies described each composition of above-mentioned table 1.Adopt plasma spray to be coated on the Q235 steel plate and prepare coating, spraying parameter is: arc voltage 70V, flame current 450A, main gas (Ar gas) 60L/min, secondary gas (H
2Gas) 30L/min, powder feed rate 50g/min, spray distance 70mm.
Fig. 1 is the surface topography of coating.As shown in Figure 1, with the coatingsurface densification behind the spray coating alloy of the present invention, evenly and tangible metalluster arranged.
Fig. 2 is the XRD diffracting spectrum of coating.As can be seen from the figure: the diffracting spectrum main body is the diffraction peak of a broadening disperse, and the top of collection of illustrative plates is a more sharp-pointed Bragg diffraction peak, illustrates that coated body is a non-crystal structure.Simultaneously, except containing amorphous, also there is crystalline material in the coating.
Fig. 3 is the TEM photo of coating.As can be seen from the figure, coating is crystalline state and amorphous mixed structure.Nanocrystalline size distribution is in formed coating, and grain-size is less than 100nm.This has illustrated the reason that has the crystallization peak among the XRD result, and crystallization has taken place for some in the promptly formed coating, has obtained the crystal grain of nano-scale.Also comprise amorphous portion in the coating, finally obtained not only containing amorphous but also contain nanocrystalline compound coating.
Coating hardness of the present invention records HV under load 100g, loading time 10s condition
0.1In 800～1200 scopes.
Adopt vertical omnipotent friction wear testing machine to carry out the unlubricated pin-type load frictional wear experiment of coating, the pin material is the 45# steel, and head is semicircle, and wearing-in period is 10 minutes.Test finds that the pin head polishes fully.Be to measure on the digital calculation balance of 0.1mg in precision with coating of the present invention, finding does not have changes in weight before and after the test, illustrates that this abrasion property can be fine.The frictional coefficient that records in the test between coating and the 45# steel column pin is 0.17, and the frictional coefficient that having of coating is low is described.
Fig. 4 is the electrokinetic potential anodic polarization curves of coating in 3.5 quality %NaCl solution, and corrosion potential is-0.49V, has tangible passivation region, and passivation current density is 7.9 * 10
- 3A/cm
2This shows that this coating has good corrosion resistance.
Claims (10)
1. iron-based amorphous nanometer crystalline coat, the composition of this coating represents to satisfy following formula with atomic ratio:
Fe
100-a-b-c-d-eNi
aCr
bP
cT
dD
e，
Wherein, a is 0.5-8, and b is 5-26, and c is 3-15, and d is that 8-20 and e are 0-8; T is selected among B, C and the Si one or more, and D is selected among Y, V, Zr, Mo, Nb, Cu, Al, Ga, Sn, W and the Mn five kinds or still less.
2. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein a is 0.5-6.
3. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein b is 7-23, is preferably 9-21.
4. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein c is 4-14, is preferably 4-13.
5. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein d is 9-18, is preferably 10-18.
6. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein e is 0-7, is preferably 0-5.
7. according to the iron-based amorphous nanometer crystalline coat of claim 1, wherein T is selected from two or three among B, C and the Si.
8. according to any one iron-based amorphous nanometer crystalline coat among the claim 1-7, wherein this coating is a hot spray coating.
9. according to any one iron-based amorphous nanometer crystalline coat among the claim 1-7, wherein this coating is an arc spraying coating.
10. according to any one iron-based amorphous nanometer crystalline coat among the claim 1-7, wherein this coating is a plasma spraying coating.
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| CN106929845A (en) * | 2017-03-30 | 2017-07-07 | 黑龙江科技大学 | It is a kind of to prepare Fe-based amorphous and nanocrystalline coating method |
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| CN110257734A (en) * | 2018-10-15 | 2019-09-20 | 天津师范大学 | Corrosion resistant iron-base amorphous alloy material and its preparation method and application |
| CN109468569A (en) * | 2018-12-29 | 2019-03-15 | 宝鸡市金得利新材料有限公司 | A kind of method of wearproof corrosion-resistant alloy coating and prepares coating |
| CN110172650A (en) * | 2019-06-18 | 2019-08-27 | 河海大学 | A kind of high anti-corrosion transformer core Fe-based amorphous/carbon nano tube compound material and its preparation method and application of low-loss |
| CN114150235A (en) * | 2020-11-30 | 2022-03-08 | 佛山市中研非晶科技股份有限公司 | Amorphous nanocrystalline master alloy and preparation method thereof |
| CN112899587A (en) * | 2021-01-15 | 2021-06-04 | 天津大学 | Corrosion-resistant iron-based amorphous alloy coating, preparation method and application thereof |
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