CN102102203B - Preparation method of corrosion resistant FeAl intermetallic compound-based composite structure coating - Google Patents
Preparation method of corrosion resistant FeAl intermetallic compound-based composite structure coating Download PDFInfo
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- CN102102203B CN102102203B CN 201010596519 CN201010596519A CN102102203B CN 102102203 B CN102102203 B CN 102102203B CN 201010596519 CN201010596519 CN 201010596519 CN 201010596519 A CN201010596519 A CN 201010596519A CN 102102203 B CN102102203 B CN 102102203B
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Abstract
The invention discloses a preparation method of a corrosion resistant FeAl intermetallic compound-based composite structure coating and relates to the fields such as material processing, metallurgy, electric power, machinery and chemical engineering. The method comprises the following steps: using cheap and common Fe, Al and ceramic particles as raw materials to prepare alloy powder through ball milling, depositing a coating on a substrate through cold spraying, preparing the FeAl intermetallic compound-based composite structure coating through heat treatment, and forming a uniform and dense Al2O3 film on the surface of the coating under a certain oxygen partial pressure. The composite structure coating prepared by the method is based on the FeAl intermetallic compound and has better high-temperature wearability and Zn (Al) corrosion resistance; and the uniform and dense Al2O3 film on the surface is used as the coating and has excellent corrosion resistance, low molten metal wettability and outstanding wearability. The coating of the invention can be widely used on the surface of the part contacting with molten metal in the industries such as zinc coating on steel.
Description
Technical field
The present invention relates to the fields such as materials processing, metallurgy, electric power, machinery, chemical industry, the parts surface that the preparation method who relates to corrosion resistant FeAl intermetallic compound-based composite structure coating, the method are particluarly suitable for contacting with liquid metal in the industry such as steel galvanization prepares refractory erosion, abrasion-resistant coatings.
Background technology
In the industries such as steel galvanization, Zn metallurgy, zinc, aluminium zinc, aluminium etc. often need to be in high-temperature liquid state, at this moment, the equipment part surface that directly contacts with high temperature fluent metal inevitably is subject to the strong corrode of liquid metal, cause parts surface to lose efficacy, thereby affect the standby continous-stable reliability service of integral installation.Take steel plate continuous zinc coating as example, the zinc liquid that contains a certain amount of aluminium generally is in the condition of high temperature more than 450 ℃, all all can be subject to the corrosion of zinc liquid with the parts surface that zinc liquid directly contacts, such as, parts surface such as sinking roller and support component thereof, zinc pot, heating unit surface, thermometric etc.Wherein, sinking roller is the vitals that directly affects the surface of steel plate galvanizing quality, is generally formed by the stainless material manufacturing, and its roll surface should keep due shape.Yet, because strong corrosion, the surface of steel plate of zinc liquid sticks to the reasons such as roll surface to wearing and tearing, the cadmia of roll surface, use the galvanizing quality that just is difficult to guarantee surface of steel plate after for some time, need to change, affect the continuous and steady operation of production line, both reduced also economic loss of production efficiency.Thereby, be very necessary at its surface preparation refractory erosion abrasion-resistant coatings.
For the problem of liquid metal corrode, more existing solutions have also obtained positive effect.EP603797 proposes to use the stupalith of the refractory erosion superior performances such as MoSi, MoB, yet these materials are difficult to the coating at sinking roller surface preparation even compact, its fragility can cause sinking roller to immerse the zinc pot and cause crackle when taking out and cause disbonding from the zinc pot, therefore, the superior refractory erosion performance of these stupaliths is difficult to be brought into play preferably.JP8104966 proposes the WC-Co metal-ceramic coating that thermospray has special composition and structure, WC has superior abrasion resistance properties and refractory erosion performance, and have refractory erosion performance and plasticity and toughness preferably take Co as main Binder Phase, therefore obtained good effect.In addition, ZL200510042321.9 adopts electric arc spraying at ferrous substrates surface preparation Al coating, surface water glass and SiO
2Carry out pyroprocessing after glaze sealing generating the FeAl intermetallic compound coating, yet the intermetallic compound that consists of due to Fe, Al two elements has multiple phase structure, the method is difficult to obtain the FeAl compound coat of the refractory erosion superior performance of homogeneous microstructure.ZL02155185.5 adopts HVOF (High Velocity Oxygen Fuel) to prepare mixolimnion and the oxide ceramic layer of FeAl intermetallic compound bottom, FeAl-oxide ceramics, prepared the gradient structure coating that consists of by three layers, have refractory erosion preferably and abrasion resistance properties, yet, the laminate structure that has intrinsic due to coating causes existing in coating perfoliate hole or crackle, molten metal may arrive the FeAl surface and cause FeAl easily by zinc liquid corrode, therefore, the failure mode that will cause that ceramic layer on surface comes off etc.
In fact, the FeAl inter-metallic compound material not only has superior refractory erosion performance, and present at 400-600 ℃ the unusual facilitation phenomenon that hardness raises with temperature, for the use in the pot galvanize operating mode, especially raise the phenomenon reduce Comparatively speaking with traditional metal alloy (such as stainless steel) hardness with temperature, also have abrasion resistance properties preferably.
Adopt hot-spraying techniques, be expected to have in the preparation of sinking roller surface spraying the FeAl inter-metallic compound material coating of good refractory erosion abrasion resistance properties.At present, in field of thermal spray, the ordinary method of preparation intermetallic compound coating has plasma spraying, hypersonic flame spraying, electric arc spraying.The key of these hot-spraying techniqueies is to make coated material fusing before arriving workpiece surface form molten drop by certain mode, and high-speed impact matrix, thereby the coating that deposition one layer tissue is finer and close and bonding strength is higher on matrix, but these technology all exist spray material before reaching workpiece surface because comparatively serious oxidation etc. occurs high temperature melting, the characteristics that prepare coating based on thermospray, the coating of formation are typical laminate structure coating.Yet the combination between these particle layers is not complete combination, but presents limited bonding state, therefore, to the bonding strength of coating, work-ing life etc. producing adverse influence, can not give full play of the performance of inter-metallic compound material.Cold spray-coating method can pass through the viscous deformation of material in remarkable condition deposit coating lower than material melting point, be expected to prepare fine and close intermetallic compound coating, yet, because intermetallic compound has significant low temperature brittleness, therefore usually adopt cold spraying to be difficult to realize effective preparation of intermetallic compound coating take intermetallic compound powder as raw material.ZL200710017976.X discloses the method that adopts ball milling metal alloy powders cold spraying and prepare intermetallic compound and eramic composite structures coating thereof in conjunction with postheat treatment, yet, although adopt the existing prepared coating of method can obtain particle strengthening effect and abrasion resistance properties preferably, but coating integral body presents the feature take FeAl as external phase, body directly has certain erosion with contacting still of molten metal to coating mutually, thereby the anti-erosion that how effectively to improve coating still requires study.
Summary of the invention
Defective or deficiency for above-mentioned technology existence, the objective of the invention is: the preparation method that a kind of new corrosion resistant FeAl intermetallic compound-based composite structure coating is provided, the coating that the method is prepared is fine and close, combination is good, have simultaneously higher refractory erosion performance and abrasion resistance properties, and have lower imbibition characteristic with zinc liquid.
General technical thinking of the present invention is: at first utilize mechanical ball milling to prepare the mechanical alloy powder that element corresponding to FeAl intermetallic compound and ceramic particle or its consists of; adopt cold spray-coating method that powder deposition is formed coating at matrix surface; then heat-treat; make alloy transform generate intermetallic compound and connect interface between the particle of coating inside by thermodiffusion, making coating formation in conjunction with intermetallic compound coating good, excellent performance.Make coatingsurface form the α-Al of the even compact of one deck under certain oxygen partial pressure condition
2O
3Film; when this oxide thickness is no more than the 5-20 micron; make that coating has refractory erosion, low molten metal infiltrates and the superior over-all properties such as wear-resistant; also can bear thermal shock; effectively avoid in addition ubiquitous penetrability hole in conventional aluminum oxide coating layer, thereby effectively protected the FeAl continuum in the composite structure coating mutually not by corrode.In fact, if form the α-Al of one deck densification in smooth FeAl matrix surface preparation
2O
3Film, this film is easy to not mate and peel off due to thermal expansion between the two.the technical program has two key points for this problem, the firstth, the feature of utilizing the cold spraying coatingsurface to present the height fluctuating makes surface film oxide present curve form rather than planeform, thereby strengthen the strain coordination ability between oxide film and matrix, the secondth, utilize in compound coating in add ceramic particle, in the coarse structure of surface film oxide and the interface zone formation of FeAl phase, add in being connected with surface film oxide ceramic particle just as tree root, surface film oxide is firmly fixed with the FeAl matrix phase in, thereby raising bonding strength, heat shock resistance and mechanical shock performance.
The present invention is achieved by following technical proposals:
The preparation method of corrosion resistant FeAl intermetallic compound-based composite structure coating, carry out as follows:
(1) Fe powder, Al powder and ceramic powder are mixed into mixed powder, wherein the atom ratio of Fe powder and Al powder is 25: 75～75: 25, the content of ceramic powder is 0%～80% of mixed powder total amount, under inert atmosphere protection, low temperature or vacuum, obtain to be distributed with by ball milling the powdered alloy that the lamellar of particulate ceramic distributes;
(2) matrix is carried out sandblast pretreatment;
(3) adopt above-mentioned powdered alloy to prepare coating with cold spray-coating method on matrix;
(4) coating being carried out 450 ℃～1300 ℃ thermal treatments makes alloy be converted into intermetallic compound;
(5) make coatingsurface that step (4) processed form the α-Al of one deck even compact under the oxygen partial pressure condition of 0.01Pa～normal pressure
2O
3Film.
Described α-Al
2O
3The thickness of film is not less than 1/3rd of ceramic particle mean sizes.
Described ceramic powder is selected from one or more in boride, carbide, oxide compound, nitride, sulfide, phosphide pottery.
Described ceramic powder is for zinc liquid or contain aluminium zinc liquid and do not infiltrate or infiltrate relatively poor stupalith.
In the preparation process of described alloy coat, thereby the employing Fe powder different from Al content obtains Fe, Al content presents step type and changes or the continually varying gradient-structure, with the combination of the thermal expansion between coordination matrix and coating and then enhancing coating and matrix.
Present step type variation or continually varying gradient-structure thereby adopt the different powder of ceramic particle content to obtain ceramic content in the preparation process of described alloy coat, with the combination of the thermal expansion between coordination matrix and coating and then enhancing coating and matrix.
The 4th step of described technical scheme omits, and changes intermetallic compound under coating 450 ℃～1300 ℃ hot conditionss in use.
Form again Al after after described the 4th step, coatingsurface being processed into required surface quality
2O
3Film.
The ceramic powder that the process of described preparation powdered alloy is added is to add with the form of ceramic precursor, generates ceramic particle at the follow-up heat treatment process situ.
The intermetallic compound base composite structure coating that method of the present invention is prepared, fully different from the laminate structure of traditional thermally sprayed coating, have inside in conjunction with good material characteristics, surface film oxide presents the characteristic of even compact, can effectively realize the characteristic of refractory erosion.Be particularly suitable at steel galvanization sinking roller surface preparation refractory erosion resisting coating.
Description of drawings
Fig. 1 is a kind of schematic diagram of coating section structure.
Fig. 2 is the schematic diagram of coating section broken covering weave structure of the present invention
The present invention is described in further detail below in conjunction with drawings and Examples.
Embodiment
Be below the specific embodiment that the contriver provides, need to prove, these embodiment are the more excellent examples of the present invention, be used for those skilled in the art and understand the present invention, but the present invention is not limited to these embodiment.
Embodiment 1:
With FeAl-Al
2O
3Be example, Fe, Al are carried out proportioning according to atomic ratio at 1: 1, and to add volume fraction be that 30% granularity is ceramic particle and the ball milling 25h of 2.5 μ m again, the powder fractography of acquisition as shown in Figure 1, Fe and Al form layers sheet distribute and are distributed with ceramic particle.At the alloy composite structure coating of sinking roller surface preparation thickness as 0.5mm, under the protection of Ar gas and 600 ℃ of conditions, coating is carried out the thermal treatment of 8h take cold spraying, make it be converted into FeAl-Al
2O
3Composite structure coating.Oxygen level in controlled atmosphere is about 20000Pa, and insulation formed the continuous α-Al of one deck even compact in 16 hours on the surface under the 1050oC condition
2O
3Film, fractography are as shown in Figure 2.
Embodiment 2:
With FeAl-Al
2O
3-MoB is example, and Fe, Al are carried out proportioning and add 25% granularity according to atomic ratio at 60: 40 is the Al of 1 μ m
2O
3Ceramic particle and 10% granularity are MoB ceramic particle and the ball milling 5h of 0.5 μ m.At the alloy composite structure coating of sinking roller surface preparation thickness as 0.3mm, under 1000 ℃ of conditions, coating is carried out the thermal treatment of 2h take cold spraying, make it be converted into FeAl-Al
2O
3-MoB composite structure coating.In heat treatment process, two kinds of elements of FeAl have diffuseed to form uniform FeAl intermetallic compound base body phase after thermal treatment.The atmosphere oxygen level of controlling hot conditions is no more than 5%, and coatingsurface can form the α-Al of even compact under the 950oC condition
2O
3Film.Under this condition, although may there be the Al of some non-α types at the upper layer of oxide film
2O
3, such as the θ-Al of needle-like or sheet
2O
3Or γ-Al
2O
3, but be still α-Al in direct and the contacted part of FeAl
2O
3, this part film plays the effect of refractory erosion, wear-resistant and low infiltration.In this case, because ceramic particle has two kinds of different yardsticks, can more be evenly dispersed in matrix, thereby make the interface roughness structure of the pellumina/FeAl phase even compact more that becomes, go up mutually just as the different tree root of thickness is locked in FeAl securely with oxide film jointly.
Embodiment 3:
On the basis of embodiment 1, Fe partly or entirely is replaced by Ni, also can obtain good effect, because the cost of Ni generally speaking is high than Fe, therefore, consider from the angle that reduces costs, Fe is preferred element.But Fe partly is replaced by Ni, perhaps adds individually or simultaneously some other elements (the various elements of sinking roller matrix alloy), can alleviate and even avoid matrix elements excessively to spread in coating, be conducive to the recycling of roll body.Based on essence technical scheme of the present invention, consider above-mentioned technical problem and will be conducive to strengthen actual implementation result of the present invention and reduce comprehensive cost.
Embodiment 4:
Only be the FeAl coating in the situation that ceramic content is zero coating for preparing, although wear resistance can be slightly low, have equally the desired good refractory of the technical program and lose effect.Fe, Al are carried out proportioning and ball milling 12h according to atomic ratio at 55: 45, obtain the powder that Fe and Al form layers sheet distribute.In the coating of sinking roller surface preparation thickness as 0.3mm, under argon gas atmosphere and 950 ℃ of conditions, coating is carried out the thermal treatment of 4h take cold spraying, make it be converted into the FeAl coating.Oxygen level in controlled atmosphere is about 10000Pa, and insulation formed the continuous α-Al of one deck even compact in 15 hours on the surface under the 1050oC condition
2O
3Film.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by claims of submitting to.
Claims (8)
1. the preparation method of corrosion resistant FeAl intermetallic compound-based composite structure coating, is characterized in that, carries out as follows:
(1) Fe powder, Al powder and ceramic powder are mixed into mixed powder, wherein the atom ratio of Fe powder and Al powder is 25:75～75:25, the content of ceramic powder by volume percentage ratio is counted 0%～80% of mixed powder total amount, under inert atmosphere protection, low temperature or vacuum, obtain to be distributed with by ball milling the powdered alloy that the lamellar of particulate ceramic distributes;
(2) matrix is carried out sandblast pretreatment;
(3) adopt above-mentioned powdered alloy to prepare coating with cold spray-coating method on matrix;
(4) coating being carried out 450 ℃～1300 ℃ thermal treatments makes alloy be converted into intermetallic compound;
(5) make coatingsurface that step (4) processed form the α-Al of one deck even compact under the oxygen partial pressure condition of 0.01Pa～normal pressure
2O
3Film;
The feature of utilizing the cold spraying coatingsurface to present the height fluctuating makes surface film oxide present curve form rather than planeform, thereby strengthens the strain coordination ability between oxide film and matrix; Utilize in compound coating in add ceramic particle, in the coarse structure of surface film oxide and the interface zone formation of FeAl phase, add ceramic particle in being connected with surface film oxide and just as tree root, surface film oxide be firmly fixed in the FeAl matrix phase.
2. the method for claim 1, is characterized in that, described α-Al
2O
3The thickness of film is not less than 1/3rd of ceramic particle mean sizes.
3. the method for claim 1, is characterized in that, described ceramic powder is selected from one or more in boride, carbide, oxide compound, nitride, sulfide, phosphide pottery.
4. the method for claim 1, is characterized in that, described ceramic powder is for zinc liquid or contain aluminium zinc liquid and do not infiltrate or infiltrate relatively poor stupalith.
5. the method for claim 1, it is characterized in that, in the preparation process of alloy coat, thereby the employing Fe powder different from Al content obtains Fe, Al content presents step type and changes or the continually varying gradient-structure, with the combination of the thermal expansion between coordination matrix and coating and then enhancing coating and matrix.
6. the method for claim 1, it is characterized in that, present step type variation or continually varying gradient-structure thereby adopt the different powder of ceramic particle content to obtain ceramic content in the preparation process of alloy coat, with the combination of the thermal expansion between coordination matrix and coating and then enhancing coating and matrix.
7. method according to claim 1, is characterized in that, forms Al after after described step (4), coatingsurface being processed into required surface quality again
2O
3Film.
8. method according to claim 1, is characterized in that, the ceramic powder that the process of preparation powdered alloy is added is to add with the form of ceramic precursor, generates ceramic particle at the follow-up heat treatment process situ.
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| CN102864317A (en) * | 2011-07-08 | 2013-01-09 | 王西临 | Sponge titanium reduction and distillation reactor sprayed with anti-oxidation layer on outer surface and spraying method |
| CN102296289A (en) * | 2011-08-19 | 2011-12-28 | 九江学院 | Preparation method of metal ceramic coating with intermetallic compound as binding phase |
| CN102443796B (en) * | 2011-12-02 | 2014-01-22 | 九江学院 | Porous Fe-Al intermetallic compound coating and its preparation method |
| CN105463444B (en) * | 2014-09-29 | 2018-10-30 | 上海宝钢工业技术服务有限公司 | Preparation method applied to sinking roller and the wear-resistant composite coating of the resistance to corrode of stabilizing roller |
| CN105734480B (en) * | 2015-12-09 | 2018-10-16 | 北京矿冶研究总院 | Method for improving corrosion resistance of lead-cooled neutron reactor structural component |
| CN107385374A (en) * | 2017-09-01 | 2017-11-24 | 海南大学 | Inserted double coatings of intermetallic compound ceramics in a kind of original position and preparation method thereof |
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| CN1757682A (en) * | 2004-10-09 | 2006-04-12 | 上海君山表面技术工程有限公司 | Metal-ceramic oxide(s) coating material, and its application |
| CN101058881A (en) * | 2007-06-04 | 2007-10-24 | 西安交通大学 | Method for preparing compound coat between metals |
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Patent Citations (3)
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| CN1757682A (en) * | 2004-10-09 | 2006-04-12 | 上海君山表面技术工程有限公司 | Metal-ceramic oxide(s) coating material, and its application |
| CN101058881A (en) * | 2007-06-04 | 2007-10-24 | 西安交通大学 | Method for preparing compound coat between metals |
| CN101545087A (en) * | 2009-04-24 | 2009-09-30 | 山东大学 | Micro-composite Fe-Al/Al2O3 ceramic coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 王洪涛等.冷喷涂FeAl金属间化合物涂层的高温磨损性能研究.《中国材料进展》.2009,第28卷(第2期),第61-64页. * |
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