CN102102203A - 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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- CN102102203A CN102102203A CN2010105965192A CN201010596519A CN102102203A CN 102102203 A CN102102203 A CN 102102203A CN 2010105965192 A CN2010105965192 A CN 2010105965192A CN 201010596519 A CN201010596519 A CN 201010596519A CN 102102203 A CN102102203 A CN 102102203A
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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 fields such as materials processing, metallurgy, electric power, machinery, chemical industry, the parts surface that the preparation method who relates to refractory erosion FeAl intermetallic compound base composite structure coating, this method are particluarly suitable for contact with liquid metal in the industry such as steel galvanization prepares that refractory loses, abrasion-resistant coatings.
Background technology
In industries such as steel galvanization, Zn metallurgy, zinc, aluminium zinc, aluminium etc. often need be in high-temperature liquid state, at this moment, be subjected to the intensive corrode of liquid metal inevitably with the equipment part surface that high temperature fluent metal directly contacts, cause parts surface to lose efficacy, thus the continous-stable reliability service of the whole equipment of influence.With steel plate continuous zinc coating is 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 subjected to the corrosion of zinc liquid with the parts surface that zinc liquid directly contacts, such as, parts surfaces such as sinking roller and support component thereof, zinc pot, heating unit surface, thermometric etc.Wherein, the sinking roller is the vitals that directly influences the surface of steel plate galvanizing quality, is generally formed by the stainless material manufacturing, and its roll surface should keep due shape.Yet, owing to strong corrosion, the surface of steel plate of zinc liquid sticks to reasons such as roll surface to roll surface wear, cadmia, use the galvanizing quality that just is difficult to guarantee surface of steel plate after for some time, need to change, influence the continous-stable operation of production line, both reduced production efficiency and also caused financial loss.Thereby, be very necessary at its surface preparation refractory erosion abrasion-resistant coatings.
At the problem of liquid metal corrode, more existing solutions have also obtained positive effect.EP603797 proposes to use the stupalith of 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, and roller immerses 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 mutually based on the bonding of Co, therefore obtained good effect.In addition, ZL200510042321.9 adopts electric arc spraying in ferrous substrates surface preparation Al coating, surface water glass and SiO
2Carry out pyroprocessing after the glaze sealing generating the FeAl intermetallic compound coating, yet because the intermetallic compound that Fe, Al two elements constitute has multiple phase structure, this 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 the mixolimnion and the oxide ceramic layer of FeAl intermetallic compound bottom, FeAl-oxide ceramics, prepared the gradient-structure coating that constitutes by three layers, have refractory erosion preferably and abrasion resistance properties, yet, because having the laminate structure of intrinsic, coating causes existing in the coating perfoliate hole or crackle, molten metal may arrive the FeAl surface and cause FeAl easily by zinc liquid corrode, therefore, will cause failure modes such as the surface ceramic pull-up falls.
In fact, the FeAl inter-metallic compound material not only has superior refractory erosion performance, and present the unusual facilitation phenomenon that hardness raises with temperature at 400-600 ℃, for the use in the pot galvanize operating mode, especially raise the phenomenon reduce Comparatively speaking with conventional metals alloy (such as stainless steel) hardness with temperature, also have abrasion resistance properties preferably.
Adopt hot-spraying techniques, be expected to have the FeAl inter-metallic compound material coating of good refractory erosion abrasion resistance properties in the spraying preparation of sinking roller surface.At present, the ordinary method of preparation intermetallic compound coating has plasma spraying, hypersonic flame spraying, electric arc spraying in the field of thermal spray.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 deposition one layer tissue is than densification and the higher coating of bonding strength on matrix, but these technology all exist spray material before reaching workpiece surface owing to comparatively serious oxidation etc. takes place high temperature melting, prepare the characteristics of coating based on thermospray, the coating of formation is typical laminate structure coating.Yet the combination between these particle layers is not complete combination, but presents limited bonding state, therefore, to Bond 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 significantly be lower than the condition deposit coating of material melting point by the viscous deformation of material, be expected to prepare fine and close intermetallic compound coating, yet, because intermetallic compound has significant low temperature brittleness, therefore be that raw material adopts cold spraying to be difficult to realize effective preparation of intermetallic compound coating usually with the intermetallic compound powder.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 existing method coatings prepared can obtain particle strengthening effect and abrasion resistance properties preferably, but it is the feature of external phase that coating integral body presents with FeAl, body directly has certain corrode with contacting still of molten metal to coating mutually, thereby the refractory erosion property that how effectively to improve coating still requires study.
Summary of the invention
Defective or deficiency at above-mentioned technology existence, the objective of the invention is: provide a kind of new refractory to lose the preparation method of FeAl intermetallic compound base composite structure coating, the coating densification that this method is prepared, combination are well, have higher refractory erosion performance and abrasion resistance properties simultaneously, 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 the corresponding element of FeAl intermetallic compound and ceramic particle or its constitutes; adopt cold spray-coating method that powder deposition is formed coating at matrix surface; heat-treat then; make alloy transform generate intermetallic compound and connect interface between the particle of coating inside by thermodiffusion, coating is formed in conjunction with intermetallic compound coating good, excellent performance.Under certain oxygen partial pressure condition, make coatingsurface form the α-Al of the even compact of one deck
2O
3Film; when this oxide thickness is no more than the 5-20 micron; make that coating has refractory erosion, low molten metal soaks into and superior over-all properties such as wear-resistant; also can bear thermal shock; effectively avoided ubiquitous penetrability hole in the conventional aluminum oxide coating layer in addition, 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, then this film is easy to not peel off owing between the two thermal expansion matches.The technical program has two key points at 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 the matrix, the secondth, utilize in the compound coating in add ceramic particle, constitute coarse structure at surface film oxide with FeAl interface zone mutually, add in being connected with surface film oxide ceramic particle just as tree root with surface film oxide firmly fix with the FeAl matrix mutually in, thereby improve bonding strength, heat shock resistance and mechanical shock performance.
The present invention is achieved by following technical proposals:
The preparation method of refractory erosion FeAl intermetallic compound base composite structure coating, carry out as follows:
(1) Fe powder, Al powder and ceramic powder are mixed into mixed powder, wherein the atom proportioning 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, be distributed with the powdered alloy of the synusia shape distribution of particulate ceramic by the ball milling acquisition;
(2) matrix is carried out sandblast pretreatment;
(3) adopt above-mentioned powdered alloy on matrix, to prepare coating with cold spray-coating method;
(4) coating being carried out 450 ℃～1300 ℃ thermal treatments makes alloy be converted into intermetallic compound;
(5) coatingsurface that step (4) was handled forms the α-Al of one deck even compact
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, the phosphide pottery.
Described ceramic powder is for zinc liquid or contain aluminium zinc liquid and do not soak into or soak into relatively poor stupalith.
Thereby adopt the Fe powder different to obtain Fe in the preparation process of described alloy coat, Al content presents step type and changes or the continually varying gradient-structure, to coordinate combining of thermal expansion between matrix and the coating and then enhancing coating and matrix with Al content.
Present step type and change or the 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, to coordinate the thermal expansion between matrix and the coating and then to strengthen combining of coating and matrix.
The 4th step of described technical scheme omits, and changes intermetallic compound under coating 450 ℃～1300 ℃ hot conditionss in use.
Form Al again 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, and original position generates ceramic particle in follow-up heat treatment process.
The intermetallic compound base composite structure coating that method of the present invention is prepared, different fully with the laminate structure of traditional hot 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 synoptic diagram of coating section structure.
Fig. 2 is the synoptic 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
Below be the specific embodiment that the contriver provides, need to prove that 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 again be that 30% granularity is ceramic particle and the ball milling 25h of 2.5 μ m, the powder fractography of acquisition as shown in Figure 1, Fe and Al form layers sheet distribute and also are distributed with ceramic particle.Is the alloy composite structure coating of 0.5mm with cold spraying at sinking roller surface preparation thickness, under Ar gas shiled and 600 ℃ of conditions coating is carried out the thermal treatment of 8h, makes it be converted into FeAl-Al
2O
3Composite structure coating.Oxygen level in the controlled atmosphere is about 20000Pa, is incubated 16 hours at surface formation one deck even compact successive α-Al under the 1050oC condition
2O
3Film, fractography are as shown in Figure 2.
Embodiment 2:
With FeAl-Al
2O
3-MoB is an example, and Fe, Al are carried out proportioning and add the Al that 25% granularity is 1 μ m according to atomic ratio at 60: 40
2O
3Ceramic particle and 10% granularity are MoB ceramic particle and the ball milling 5h of 0.5 μ m.Is the alloy composite structure coating of 0.3mm with cold spraying at sinking roller surface preparation thickness, under 1000 ℃ of conditions coating is carried out the thermal treatment of 2h, makes 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 control 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 needle-like or flaky θ-Al
2O
3Or γ-Al
2O
3, but directly and the contacted part of FeAl still be α-Al
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 be evenly dispersed in the matrix more, 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 generally speaking therefore the cost of Ni, considers that from the angle that reduces cost Fe is preferred element than the Fe height.But Fe partly is replaced by Ni, perhaps adds some other elements (the various elements of sinking roller matrix alloy) individually or simultaneously, can alleviate even avoid the matrix alloy element excessively in coating, to spread, help the utilization again of roll body.Based on essence technical scheme of the present invention, take all factors into consideration above-mentioned technical problem and will help strengthening actual implementation result of the present invention and reduce comprehensive cost.
Embodiment 4:
Be that the coating for preparing under zero the situation only is the FeAl coating in ceramic content,, have the desired good refractory erosion effect of the technical program equally although wear resistance can be low slightly.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.Is the coating of 0.3mm with cold spraying at sinking roller surface preparation thickness, under argon gas atmosphere and 950 ℃ of conditions coating is carried out the thermal treatment of 4h, makes it be converted into the FeAl coating.Oxygen level in the controlled atmosphere is about 10000Pa, is incubated 15 hours at surface formation one deck even compact successive α-Al under the 1050oC condition
2O
3Film.
Above content is to further describing that the present invention did in conjunction with concrete preferred implementation; 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 being submitted to.
Claims (9)
1. the preparation method of refractory erosion FeAl intermetallic compound base 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 proportioning 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, be distributed with the powdered alloy of the synusia shape distribution of particulate ceramic by the ball milling acquisition;
(2) matrix is carried out sandblast pretreatment;
(3) adopt above-mentioned powdered alloy on matrix, to prepare coating with cold spray-coating method;
(4) coating being carried out 450 ℃～1300 ℃ thermal treatments makes alloy be converted into intermetallic compound;
(5) coatingsurface that step (4) was handled forms the α-Al of one deck even compact
2O
3Film.
2. as claims 1 described method, it is characterized in that described α-Al
2O
3The thickness of film is not less than 1/3rd of ceramic particle mean sizes.
3. as claims 1 described method, it is characterized in that described ceramic powder is selected from one or more in boride, carbide, oxide compound, nitride, sulfide, the phosphide pottery.
4. as claims 1 described method, it is characterized in that described ceramic powder is for zinc liquid or contain aluminium zinc liquid and do not soak into or soak into relatively poor stupalith.
5. as claims 1 described method, it is characterized in that, thereby adopt the Fe powder different to obtain Fe in the preparation process of described alloy coat, Al content presents step type and changes or the continually varying gradient-structure, to coordinate combining of thermal expansion between matrix and the coating and then enhancing coating and matrix with Al content.
6. as claims 1 described method, it is characterized in that, present step type and change or the 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, to coordinate the thermal expansion between matrix and the coating and then to strengthen combining of coating and matrix.
7. as claims 1 described method, it is characterized in that described step (4) is omitted, and changes intermetallic compound under coating 450 ℃～1300 ℃ hot conditionss in use.
8. according to claims 1 described method, it is characterized in that, form Al again after after the described step (4) coatingsurface being processed into required surface quality
2O
3Film.
9. according to claims 1 described method, it is characterized in that the ceramic powder that the process of described preparation powdered alloy is added is to add with the form of ceramic precursor, original position generates ceramic particle in follow-up heat treatment process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296289A (en) * | 2011-08-19 | 2011-12-28 | 九江学院 | Preparation method of metal ceramic coating with intermetallic compound as binding phase |
| CN102443796A (en) * | 2011-12-02 | 2012-05-09 | 九江学院 | Porous Fe-Al intermetallic compound coating and its preparation method |
| 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 |
| CN105463444A (en) * | 2014-09-29 | 2016-04-06 | 上海宝钢工业技术服务有限公司 | Preparation method for corrosion-resistant anti-abrasion composite coating |
| CN105734480A (en) * | 2015-12-09 | 2016-07-06 | 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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2010
- 2010-12-20 CN CN 201010596519 patent/CN102102203B/en not_active Expired - Fee Related
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102443796A (en) * | 2011-12-02 | 2012-05-09 | 九江学院 | Porous Fe-Al intermetallic compound coating and its preparation method |
| CN102443796B (en) * | 2011-12-02 | 2014-01-22 | 九江学院 | Porous Fe-Al intermetallic compound coating and its preparation method |
| CN105463444A (en) * | 2014-09-29 | 2016-04-06 | 上海宝钢工业技术服务有限公司 | Preparation method for corrosion-resistant anti-abrasion composite coating |
| 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 |
| CN105734480A (en) * | 2015-12-09 | 2016-07-06 | 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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