CN103866223A - Novel tough particle strengthened iron-based amorphous composite coating - Google Patents
Novel tough particle strengthened iron-based amorphous composite coating Download PDFInfo
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- CN103866223A CN103866223A CN201310444641.1A CN201310444641A CN103866223A CN 103866223 A CN103866223 A CN 103866223A CN 201310444641 A CN201310444641 A CN 201310444641A CN 103866223 A CN103866223 A CN 103866223A
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Abstract
The invention provides a novel tough particle strengthened iron-based amorphous composite coating. The mechanical composite powder of iron-based amorphous alloy powder and tough metal powder is used as a raw material, wherein the iron-based amorphous alloy powder consists of the following elements and unavoidable impurities in percentage by atom: 10.0-17.0% of Cr, 12.0-20.0% of Mo, 4.0-8.0% of B, 10.0-18.0% of C, 0.0-5.0% of Y and the balance of Fe; the tough metal powder can be stainless steel powder, nickel-based metal powder, cobalt-based metal powder, aluminum-based metal powder or copper-based alloy powder; the coating is prepared by the high velocity oxy-fuel technology. The iron-based amorphous composite coating provided by the invention has dense structure, low porosity, relatively high toughness and good bonding strength with the metal substrate. The composite coating has great application prospects in the industrial fields such as waterpower and oil-gas field development facilities, pipeline transportation, ship decks and the like.
Description
Technical field
The present invention relates to a kind of Fe-based amorphous base composite coating and prepare the method for this compound coating, belong to compound coating field.
Background technology
Hypersonic flame spraying (HVOF) is a kind of spraying technology occurring the eighties in last century, mainly utilize the Lavalle curve design of combustion chamber end, combustion chamber pressure is increased, the speed that is several times as much as velocity of sound of the flame filariasis by this place, flame temperature reaches 2500 DEG C.Coating porosity prepared by hypersonic flame spraying is low, hardness is high, and coat-thickness can reach several mm, therefore obtains widespread uses at many industrial sectors.Supersonic spray coating powdered material used adopts gas atomization to obtain mostly, and gas atomization is mainly to utilize high velocity air and the high-speed liquid metal flow that impacts, and makes it be atomized into small droplets, is frozen into subsequently powder.Gained powder size is more concentrated, and powder pick-up rate is high, and spheroidization degree is good, and amorphous powdered alloy used for hot spraying adopts gas atomization to make mostly at present.
The iron base amorphous alloy coatings that amorphous alloy coating, especially cost are relatively cheap, has extraordinary physics and chemistry performance, as the hardness of superelevation and splendid wear-resisting corrosion-resistant energy, therefore has broad application prospects in Surface Engineering field.But single iron base amorphous alloy coatings and metallic matrix show relatively low bonding strength with and intrinsic fragility, this has not only affected its military service performance and work-ing life, has more greatly limited its industrial application.Therefore the amorphous alloy-based coating of developing the high bond strength of toughness just seems significant.At present there is not yet in the world open report about the research of the Fe-based amorphous base composite coating of stainless steel granule enhancement type and mechanical property thereof.
Summary of the invention
The object of the present invention is to provide a kind of toughness, there is the Fe-based amorphous base composite coating of good combination intensity with metallic matrix, to solve current single-phase iron base amorphous alloy coatings bonding strength low, the shortcoming of poor ductility.Meanwhile, the present invention also provides the preparation method of the Fe-based amorphous base composite coating of a kind of novel high adhesion strength.
Technical scheme of the present invention is:
A kind of Fe-based amorphous base composite coating of novel toughness particle strengthening, taking Fe-based amorphous alloy powder as initial powder, add tough metal powder, make composite powder through low energy ball milling, adopt hypersonic flame spraying technology to prepare Fe-based amorphous base composite coating taking it as raw material, wherein, described tough metal powder adopts: powder of stainless steel, nickel based metal powder, powder metal composition, aluminium based metal powder, one or more powder mixs in copper base metal powder; Described Fe-based amorphous alloy powder forms (atomic percent) by following element and inevitable impurity:
Cr10.0～17.0；
Mo12.0～20.0；
C10.0～18.0；
B4.0～8.0；
Y0.0-5.0；
Fe surplus.
Preferably, described Stainless Steel Powder material is 316,316L or 304; Described nickel based metal powdered material is NiCrAl, NiAl, NiCr, NiP or pure Ni; Described powder metal composition material is CoNi, CoAl or pure Co; Described aluminium based metal powdered material is AlNi; Described copper base metal powdered material is CuNi, CuCo or pure Cu.
Preferably, ultrasonic gas atomization technology preparation for described Fe-based amorphous alloy powder, its particle size range is 20-55 μ m, powder is complete non-crystalline state.
Preferably, the particle size range of described tough metal powder is 20-55 μ m, and powder is crystalline state.
Preferably, the massfraction of described tough metal powder is at 0-30%.
Preferably, the porosity of described compound coating is lower than 1%.
Preferably, the bonding strength of described compound coating and metal base is greater than 40MPa.
Preferably, the bending fracture strain of described compound coating reaches more than 0.73%.
Preferably, described compound coating adopts the preparation of hypersonic flame spraying technology, and spraying parameter used is: kerosene oil flow 20-26l/h, oxygen flow 30-36m
3/ h, spray distance 200-350mm, powder feeding rate 20-40g/min.
Beneficial effect of the present invention is as follows:
1) the present invention has selected a kind of Fe-based amorphous composition with high rigidity, non-metallic element C, and B, Si makes it have good glass forming ability and high rigidity, and this cost of alloy is cheap, is easy to suitability for industrialized production; In addition, the amorphous powder of preparation has extraordinary mobility, is well suited for utilizing spraying coating process to prepare coating.
2) the present invention selects tough metal powder as toughness wild phase, powder of stainless steel (316,316L, 304 etc.), nickel based metal powder (NiCrAl, NiAl, NiCr, NiP, pure Ni etc.), powder metal composition (CoNi, CoAl, pure Co etc.), aluminium based metal powder (AlNi etc.), copper base metal powder (CuNi, CuCo, pure Cu etc.) in one or more powder mixs, it is lower that fusing point sprays flame temperature relatively, under high strain rate, there is good plastic deformation ability, can fully be out of shape and form fine and close coating structure.Because spraying flame temperature is higher than powder particle fusing point, these tough metal powder in spraying process can with amorphous powdered alloy generation metallurgical binding, strengthen coating cohesion, and in coating experiencing a shock while deforming, energy Anticrack, self there is moulding distortion absorption portion ballistic work, improve deformability and the impact resistance of Bulk coat.
3) iron-based amorphous coating that the present invention obtains, is keeping on the basis of traditional amorphous alloy coating high rigidity, and more than the bonding strength between coating and matrix is brought up to 40MPa, breaking strain reaches more than 0.73%.Excellent toughness and make this compound coating have great application prospect in fields such as boats and ships, waterpower and oil-gas field development facility, pipeline transportation, ship decks with the high bonding strength of matrix.
Brief description of the drawings
Fig. 1 is for adopting 316L powdered alloy, the X-ray diffraction result figure of single-phase iron base amorphous alloy coatings prepared by hypersonic flame spraying technology and Fe-based amorphous base composite coating;
Fig. 2 is scanning electronic microscope (SEM) the Cross Section Morphology figure of the Fe-based amorphous base composite coating prepared of hypersonic flame spraying technology;
Fig. 3 is the bonding strength data of single-phase iron base amorphous alloy coatings and the Fe-based amorphous base composite coating that contains different 316L massfractions;
Fig. 4 is the single-phase iron base amorphous alloy coatings prepared of hypersonic flame spraying technology and the stress in bending strain curve figure of Fe-based amorphous base composite coating.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
First make mother alloy by required composition by the method for vacuum induction melting, alloying constituent is Fe48.5Mo13.5Cr15.3Y2C14.5B6.2(at.%), mother alloy is put into atomizing furnace, prepare amorphous powdered alloy by gas atomization technology.By the 316L powder of stainless steel of massfraction 9%, be blended in amorphous powdered alloy, evenly mix through low energy ball milling, make composite powder raw material.Described 316L powder of stainless steel is commercially available prod, and powder diameter is 20-55um.
Adopt hypersonic flame spraying technology to prepare Fe-based amorphous base composite coating, concrete spraying parameter is: kerosene oil flow 20l/h
-1, oxygen flow 36m
3/ h
-1, spray distance 300mm, powder feeding rate 25g/min
-1.As shown in Figure 1, prepared amorphous base composite coating main body is still non-crystal structure, and crystallization peak is powder of stainless steel characteristic peak.
This coating adopts 316L as toughness reinforcing phase, prepared Fe-based amorphous base composite coating, and compact structure, porosity is lower than 1%, as shown in Figure 2 a.
Utilize micro Vickers to measure the hardness value of this compound coating, exert pressure is 300g, and the time length is 10s, and 10 numerical value of each sample test different zones, average.Coating hardness reaches 830HV.
Testing the bonding strength of Fe-based amorphous base composite coating with ASTMC633 standard method, find that the bonding strength of this Fe-based amorphous base composite coating reaches 44MPa, is 1.7 times of single-phase amorphous alloy coating bonding strength, as shown in Figure 3.
Obtain the stress-strain(ed) curve of Fe-based amorphous base composite coating with three-point bending method, find that the breaking strain of the composite amorphous coating of this iron-based reaches shown in 0.73%(Fig. 4), be 1.8 times of single-phase iron base amorphous alloy coatings, corresponding work of rupture is also by from 215J/m
2bring up to 310J/m
2.
Embodiment 2
This embodiment difference from Example 1 is:
(1) the 316L powder of stainless steel massfraction that the compound coating that prepared by the present embodiment contains is 16%, as shown in Figure 2 b;
(2) microhardness of the compound coating that prepared by the present embodiment is 794Hv;
(3) bonding strength of the compound coating that prepared by the present embodiment reaches 45MPa, as shown in Figure 3;
(4) flexural strain of the compound coating that prepared by the present embodiment reaches 0.90%, as shown in Figure 4.
Embodiment 3
This embodiment difference from Example 1 is:
(1) it is 20% nickel based metal powder (Cr17Al5, Ni surplus) that the compound coating that prepared by the present embodiment contains massfraction;
(2) the present embodiment spraying parameter is: kerosene oil flow 22l/h
-1, oxygen flow 36m
3/ h
-1, spray distance 350mm, powder feeding rate 22g/min
-1;
(3) the compound coating bonding strength that prepared by the present embodiment is 46MPa;
(4) the compound coating porosity that prepared by the present embodiment is lower than 0.7%.
Those skilled in the art should know, and the toughness particle for strengthening using in the present invention is not limited in 316L powder of stainless steel and the nickel based metal powder (Cr17Al5, Ni surplus) of embodiment.Powder of stainless steel (316, 316L, 304 etc.), nickel based metal powder (NiCrAl, NiAl, NiCr, NiP, pure Ni etc.), powder metal composition (CoNi, CoAl, pure Co etc.), aluminium based metal powder (AlNi etc.), copper base metal powder (CuNi, CuCo, pure Cu etc.) all there is good ductility and toughness, and melt temperature is lower than spraying flame temperature, under high strain rate, can fully be out of shape and form fine and close coating structure, with amorphous powdered alloy generation metallurgical binding, strengthen coating cohesion, and experiencing a shock in coating, when distortion, energy Anticrack, self there is moulding distortion absorption portion ballistic work, improve deformability and the impact resistance of Bulk coat.Powder of stainless steel (316,316L, 304 etc.), nickel based metal powder (NiCrAl, NiAl, NiCr, NiP, pure Ni etc.), powder metal composition (CoNi, CoAl, pure Co etc.), aluminium based metal powder (AlNi etc.), copper base metal powder (CuNi, CuCo, pure Cu etc.) can be used as toughness enhanced granule, in order to improve the bonding strength of Fe-based amorphous base composite coating, ductility and toughness.
In addition, the Fe-based amorphous alloy powder adopting in the present invention does not limit in the above-described embodiments several, elementary composition wherein and content can be selected according to specific needs, and in the present invention, the component of each element meets following ranges all can realize technique effect of the present invention.Be specially: it forms (atomic percent) by following each component and inevitable impurity:
Cr10.0～17.0；
Mo12.0～20.0；
C10.0～18.0；
B4.0～8.0；
Y0.0-5.0；
Fe surplus.
The above; only for preferably embodiment of the present invention, but the scope of protection of the invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. the Fe-based amorphous base composite coating of a novel toughness particle strengthening, it is characterized in that: taking Fe-based amorphous alloy powder as initial powder, add tough metal powder, make composite powder through low energy ball milling, adopt hypersonic flame spraying technology to prepare Fe-based amorphous base composite coating taking it as raw material, wherein, described tough metal powder adopts: powder of stainless steel, nickel based metal powder, powder metal composition, aluminium based metal powder, one or more powder mixs in copper base metal powder; Described Fe-based amorphous alloy powder forms (atomic percent) by following element and inevitable impurity:
Cr10.0～17.0；
Mo12.0～20.0；
C10.0～18.0；
B4.0～8.0；
Y0.0-5.0；
Fe surplus.
2. compound coating according to claim 1, is characterized in that: described Stainless Steel Powder material is 316,316L or 304; Described nickel based metal powdered material is NiCrAl, NiAl, NiCr, NiP or pure Ni; Described powder metal composition material is CoNi, CoAl or pure Co; Described aluminium based metal powdered material is AlNi; Described copper base metal powdered material is CuNi, CuCo or pure Cu.
3. compound coating according to claim 1 and 2, is characterized in that: ultrasonic gas atomization technology preparation for described Fe-based amorphous alloy powder, and its particle size range is 20-55 μ m, powder is complete non-crystalline state.
4. compound coating according to claim 1 and 2, is characterized in that: the particle size range of described tough metal powder is 20-55 μ m, and powder is crystalline state.
5. compound coating according to claim 1 and 2, is characterized in that: the massfraction of described tough metal powder is at 0-30%.
6. compound coating according to claim 1 and 2, is characterized in that: the porosity of described compound coating is lower than 1%.
7. compound coating according to claim 1 and 2, is characterized in that: the bonding strength of described compound coating and metal base is greater than 40MPa.
8. compound coating according to claim 1 and 2, is characterized in that: the bending fracture strain of described compound coating reaches more than 0.73%.
9. compound coating according to claim 1, is characterized in that: described compound coating adopts the preparation of hypersonic flame spraying technology, and spraying parameter used is: kerosene oil flow 20-26l/h, oxygen flow 30-36m
3/ h, spray distance 200-350mm, powder feeding rate 20-40g/min.
10. a method of preparing the compound coating as described in claim 1-9, is characterized in that: comprise the following steps:
First make mother alloy by required composition by the method for vacuum induction melting, mother alloy is put into atomizing furnace, prepare amorphous powdered alloy by gas atomization technology, add tough metal powder, make composite powder through low energy ball milling, adopt hypersonic flame spraying technology to prepare Fe-based amorphous base composite coating taking it as raw material, wherein, described tough metal powder adopts: powder of stainless steel, nickel based metal powder, powder metal composition, aluminium based metal powder, one or more powder mixs in copper base metal powder; Described Fe-based amorphous alloy powder forms (atomic percent) by following element and inevitable impurity:
Cr10.0～17.0；
Mo12.0～20.0；
C10.0～18.0；
B4.0～8.0；
Y0.0-5.0；
Fe surplus;
Wherein, adopt hypersonic flame spraying technology to prepare Fe-based amorphous base composite coating, concrete spraying parameter is: kerosene oil flow 20l/h
-1, oxygen flow 36m
3/ h
-1, spray distance 300mm, powder feeding rate 25g/min
-1.
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| CN104233119A (en) * | 2014-09-15 | 2014-12-24 | 华中科技大学 | Corrosion-resistant wear-resistant iron-based amorphous thin film and preparation method thereof |
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