CN103789713A - Anti-oxidation MCrAlY fine-grain protective coating material and preparation method thereof - Google Patents
Anti-oxidation MCrAlY fine-grain protective coating material and preparation method thereof Download PDFInfo
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- CN103789713A CN103789713A CN201410046231.6A CN201410046231A CN103789713A CN 103789713 A CN103789713 A CN 103789713A CN 201410046231 A CN201410046231 A CN 201410046231A CN 103789713 A CN103789713 A CN 103789713A
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Abstract
The invention relates to the technical field of coatings, and particularly relates to an anti-oxidation MCrAlY fine-grain protective coating material and a preparation method thereof. The anti-oxidation MCrAlY fine-grain protective coating material comprises a high-temperature alloy matrix, an MCrAlY protective coating, and a super-fine grain remelting layer. The invention further discloses a preparation method of the anti-oxidant MCrAlY fine-grain protective coating material, namely, an MCrAlY protective coating with a super-fine grain structure is prepared by adopting an air plasma spraying (APS) and high current pulsed electron beam (HCPEB) compounding technology. The MCrAlY protective coating with the super-fine grain structure, prepared by adopting the compounding technology, is capable of accelerating selective oxidation of an Al element, and promoting the coating to rapidly form a continuous and compact oxidation film within a short time, thereby reducing the consumption of an oxidation film generating element in the oxidation process, and further improving the anti-oxidation capacity of the coating.
Description
Technical field
The present invention relates to coating technology field, relate in particular to thin brilliant barrier material of a kind of anti-oxidant MCrAlY and preparation method thereof.
Background technology
In fields such as modern energy and Aeronautics and Astronautics industry, for improving the performance index of power system, the performance of superalloy and barrier material thereof is proposed to more and more higher requirement; In actual applications, superalloy mainly plays carry load effect, protective coating plays the effect of opposing high temperature oxidation, therefore, measures the pyro-oxidation resistance of barrier material, the improvement approach of studying its oxidation and failure mechanism, searching high temperature oxidation resistance just seems particularly urgent.
(M is magnesium-yttrium-transition metal Ni, Co to MCrAlY, or the mixture of Ni and Co) coating is owing to having good resistance to high temperature oxidation and heat and corrosion resistant performance, and be widely used in and make the antioxidant defense coating and the heat barrier coating bonding layer that run on the gas turbine blades that parameter is high, environment for use is severe; The preparation technology of coating has multiple, comprises electro beam physics vapour deposition (EB-PVD), plasma spraying (PS), detonation flame spraying (DS) and high speed oxygen flame plating (HVOF) etc.; The advantages such as wherein, plasma spraying technology is low owing to having cost, and production efficiency is high, and coating thickness variable range is large, and composition is easy to control become the main preparation methods of MCrAIY protective coating; But in coating prepared by plasma spraying, there is more loose and hole and laminated structure interface, all may become the passage that the element such as oxygen, sulphur is invaded, and then affect formation and the growth of oxide film, finally cause coating easily ftracture or come off.
For a long time, the research work of protective coating is all carried out from preparation process amelioration and coating structure control two aspects, to realize the target of improving antioxidant property; But the factors such as the complicacy of following in process modification process, stability and economy have greatly restricted its widespread use in coating technology field; And by contrast, structure control has the tiny coating of compounding technology acquisition crystal grain of thinning microstructure characteristic method as utilized can overcome the above problems well.
Consider based on above technology, the invention discloses thin brilliant barrier material of a kind of resistance to oxidation MCrAlY and preparation method thereof; Utilize the preparation of " air plasma spraying (APS)+high-current pulsed electron beam (HCPEB) " compounding technology to there is the MCrAlY protective coating of ultra-fine grained structure; This refinement coating structure, can accelerate the selective oxidation of Al element, impel coating to form fast in a short period of time fine and close continuously oxide film, thereby reduce the consumption of oxide film generting element in oxidising process, and then improve the resistance of oxidation of coating.This thin brilliant protective coating is a kind of desirable oxidation resistant coating material.
Summary of the invention
In order to solve the technical problem existing in background technology, the present invention proposes thin brilliant barrier material of a kind of resistance to oxidation MCrAlY and preparation method thereof.Utilize " air plasma spraying (APS)+high-current pulsed electron beam (HCPEB) " compounding technology, not only overcome plasma spraying method and prepared the deficiency of coating, be that prepared coating is loose, porous, and surface irregularity, phase structure are inhomogeneous, easily cause coating shedding; Can obtain the coating structure of refinement, and then improve the resistance of oxidation of coating simultaneously.
The thin brilliant barrier material of a kind of resistance to oxidation MCrAlY that the present invention proposes, comprise superalloy matrix, form MCrAlY protective coating at described superalloy matrix surface, form Ultra-fine Grained remelted layer on described MCrAlY protective coating surface, described surperficial MCrAlY protective coating adopts air plasma spraying method to obtain, and described Ultra-fine Grained remelted layer adopts high-current pulsed electron beam Technology For Remelting to be prepared from.
MCrAlY(M prepared by described plasma spraying is Ni, Co, or the mixture of Ni and Co), coat-thickness is between 150-200 μ m.
Thin brilliant protective coating prepared by described high-current pulsed electron beam Technology For Remelting, smooth surface, densification, be uniform-distribution with a large amount of ultra-fine grained structures, and grain-size is between 40-500 nm.
In the present invention, the thin brilliant barrier material of above-mentioned disclosed MCrAlY compared with prior art, have the following advantages: the coatingsurface that utilizes electron beam microstructure of plasma sprayed method to prepare carries out remelting processing, and coatingsurface forms the remelted layer of smooth densification, thickness can reach tens microns; Meanwhile, beam bombardment causes coating top layer fusing cooling fast, and in process of setting very fast, crystal grain has little time to grow up, thereby forms ultra-fine grained structure at irradiation surface.These ultra-fine grained structures can provide a large amount of diffusion admittances for the diffusion of Al element, accelerate its selective oxidation, and form fast one deck α-Al of densification continuously at the oxidation initial stage
2o
3protective membrane, thus make coating there is the time shorten of anti-oxidant steady state period and guarantee that the consumption of oxide film generting element in oxidising process is very little, and then effectively improve the resistance of oxidation of coating.
The preparation method who the invention allows for the thin brilliant barrier material of a kind of resistance to oxidation MCrAlY, comprises the following steps:
(1) superalloy matrix, after pre-grinding, cleaning, sandblast roughening treatment, utilizes the method for air plasma spraying at superalloy matrix surface deposition MCrAlY protective coating;
(2) the MCrAlY protective coating preparing is carried out to HCPEB bombardment processing, realize MCrAlY coatingsurface remelting processing, complete the preparation of the thin brilliant protective coating of MCrAlY.
(3) the thin crystal coating sample preparing is carried out to high temperature oxidation resistance and detect analysis, detect stopping property and high-temperature oxidation.
The atmospheric plasma spraying technology adopting in described step (1), selection voltage is 33 ~ 40V, and electric current is 720 ~ 820A, and powder sending quantity is 2 ~ 5rmp, and sandblast speed is 400 ~ 500mm/s, spray distance is 80 ~ 100mm.
The HCPEB Technology For Remelting adopting in described step (2), selects vacuum tightness P≤8 × 10
-3pa, beam energy is 20 ~ 40 KeV, energy density is 3 ~ 10 J/cm
2, bombardment number of times is 10 ~ 50 times, target spacing is from being 15 ~ 20cm.
The guiding theory of technique scheme is: Intense Pulsed Relativistic Electron Beam and material surface interactions are a rapid heating and quick cooling process, and rate of heating is up to 10
9k/s, can be by the instantaneously heating of material surface certain depth to fusing, the very big thermograde (10 of formation
7～8k/m) can make upper layer sharply cooling by the thermal conduction to matrix, speed of cooling also reaches 10
4～9k/s, thus make solid material surface remelting; In addition,, under curing condition very fast, a large amount of forming cores of melt that electron beam irradiation produces but crystal grain have little time to grow up, thereby form ultra-fine grained structure on irradiation top layer.
In the present invention, the preparation method of the thin brilliant barrier material of above-mentioned disclosed resistance to oxidation MCrAlY compared with prior art, have the following advantages: HCPEB irradiation is pure energy transportation process, compared with the effect of laser beam, pulsed ionizing beam, not only overcome ionic impurity that pulsed ionizing beam irradiation the brings problem that affects on material, because the quality of electronics is very little, therefore much larger than the modified layer degree of depth of ionic fluid, and will exceed much than the capacity usage ratio of laser beam; Utilize the above-mentioned advantage of HCPEB to carry out surface remelting processing to the MCrAlY protective coating of air plasma spraying, adjust electron beam parameter and make to obtain ultrafine-grained (UFG) microstructure after coatingsurface remelting, this thin brilliant protective coating has good high temperature oxidation resistance.
Accompanying drawing explanation
Fig. 1 is the surperficial sem analysis figure of the thin brilliant barrier material of a kind of resistance to oxidation MCrAlY in the present invention;
Fig. 2 is the sem analysis figure of Fig. 1 floating coat surface ultra-fine grained structure;
Fig. 3 is the sem analysis figure of Fig. 1 floating coat cross section remelted layer;
Fig. 4 is the sem analysis figure of the continuous Oxide Film Surface Appearance of Fig. 1 floating coat isothermal oxidation 100 h rear interface places formation.
Embodiment
Embodiment 1: describe the embodiment of the thin brilliant protective coating high temperature oxidation resistent susceptibility of CoCrAlY in detail in conjunction with concrete experimentation, take identical energy, different pulse number as example, concrete steps are as follows:
(1) preparation of the thin brilliant protective coating of CoCrAlY
S1, superalloy matrix, the parts such as such as engine blade, after pre-grinding, cleaning, sandblast roughening treatment, utilize the method for air plasma spraying at superalloy matrix surface deposition Co23Cr13Al0.5Y protective coating, and thickness is at 200 μ m; Selecting voltage according to the technical requirements of air plasma spraying equipment is 38 V, and electric current is 750 A, and spray gun speed is 450 mm/s, and spray distance is 85 mm.
S2, the Co23Cr13Al0.5Y protective coating preparing is fixed on the sample bench of high-current pulsed electron beam (HCPEB) device, closes vacuum chamber and vacuumize, vacuum tightness P≤8 × 10
-3pa;
S3, the Co23Cr13Al0.5Y protective coating preparing is carried out to HCPEB bombardment processing; Selecting beam energy according to the technical requirements of HCPEB equipment is 27 KeV, and energy density is 4 J/cm
2, target spacing, from being 15 cm, carries out radiation treatment 1,5,10,20 and 30 times to sample, realizes coatingsurface remelting processing, completes the preparation of the thin brilliant protective coating of Co23Cr13Al0.5Y.
(2) high temperature oxidation resistance test
S4, the thin brilliant protective coating preparing is placed in the box heat treatment furnace of sealing, in normal pressure still air atmosphere 1050
oisothermal oxidation 100 h under C.
Thin brilliant protective coating surface phase structure is carried out to XRD test; Result demonstration, coatingsurface phase structure is fairly simple, mainly comprises γ-Co, β-CoAl and α-Al
2o
3; Along with the increase of bombardment number of times, there is not obvious variation in peak position, illustrates and do not have obvious unrelieved stress to produce.
Thin brilliant protective coating surface topography is carried out to SEM observation; Result demonstration, after 1 bombardment, coatingsurface is realized remelting; After multiple pulses number of times bombardment processing, smooth after material surface remelting, fine and close, along with the increase of bombardment number of times, remelted layer thickness constantly increases; In addition, be uniform-distribution with a large amount of ultra-fine grained structures on remelted layer top layer.
Thin brilliant protective coating oxidation resistent susceptibility is carried out to high temperature test; Static oxidization demonstration at 1050 ℃, this thin brilliant protective coating oxide on surface is mainly α-Al
2o
3, the spinel strucutre oxides that contains minute quantity.Cross Section Morphology is observed and is shown, oxide film is evenly continuous, and along with bombarding the increase of number of times, the thickness of oxide film constantly reduces.
Embodiment 2: describe the embodiment of the thin brilliant protective coating high temperature oxidation resistent susceptibility of Co23Cr13Al0.5Y in detail in conjunction with concrete experimentation, take identical pulse number of times, different-energy as example, concrete steps are as follows:
(1) preparation of the thin brilliant protective coating of Co23Cr13Al0.5Y
S1, superalloy matrix parts such as (or) engine blades, after pre-grinding, cleaning, sandblast roughening treatment, utilize the method for air plasma spraying at superalloy matrix deposition Co23Cr13Al0.5Y protective coating, and thickness is at 200 μ m; Selecting voltage according to the technical requirements of air plasma spraying equipment is 38 V, and electric current is 750 A, and spray gun speed is 450 mm/s, and spray distance is 85 mm.
S2, the Co23Cr13Al0.5Y protective coating preparing is fixed on the sample bench of high-current pulsed electron beam (HCPEB) device, closes vacuum chamber and vacuumize, vacuum tightness P≤8 × 10
-3pa;
S3, the Co23Cr13Al0.5Y protective coating preparing is carried out to HCPEB bombardment processing.Selecting beam energy according to the technical requirements of HCPEB equipment is 21.6,23.4 and 27 KeV, and energy density is 4 J/cm
2, target spacing, from being 15 cm, carries out radiation treatment 20 times to sample, realizes Co23Cr13Al0.5Y coatingsurface remelting processing, completes the preparation of the thin brilliant protective coating of Co23Cr13Al0.5Y.
(2) high temperature oxidation resistance test
S4, the thin brilliant protective coating preparing is placed in the box heat treatment furnace of sealing, in normal pressure still air atmosphere 1050
oisothermal oxidation 100 h under C.
Thin brilliant protective coating surface phase structure is carried out to XRD test; Result demonstration, coatingsurface phase structure is fairly simple, mainly comprises γ-Co, β-CoAl and α-Al
2o
3; Along with the increase of beam energy, there is not obvious variation in peak position, illustrates and do not have obvious unrelieved stress to produce.
Thin brilliant protective coating surface topography is carried out to SEM observation; Result shows, after different beam energy bombardment processings, smooth after material surface remelting, fine and close, and along with the continuous increase of beam energy, remelted layer thickness constantly increases; In addition, be uniform-distribution with a large amount of ultra-fine grained structures on remelted layer top layer.
Thin brilliant protective coating oxidation resistent susceptibility is carried out to high temperature test; Static oxidization demonstration at 1050 ℃, this thin crystal coating oxide on surface is mainly α-Al
2o
3, the spinel strucutre oxides that contains minute quantity.Cross Section Morphology is observed and is shown, oxide film is evenly continuous, and along with the increase of beam energy, the thickness of oxide film constantly reduces.
The thin brilliant barrier material of MCrAlY obtaining in embodiment 1-2 has three-decker, is respectively matrix, MCrAlY coating, thin brilliant remelted layer, and its sem analysis figure as Figure 1-3; Fig. 1 is the surperficial sem analysis figure of the thin brilliant protective coating of resistance to oxidation MCrAlY; Fig. 2 is the sem analysis figure of Fig. 1 floating coat surface ultra-fine grained structure; Fig. 3 is the sem analysis figure of Fig. 1 floating coat cross section remelted layer; Result shows, the coated material top layer that this kind of compounding technology is prepared from is smooth, fine and close, and ultra-fine grained structure size is probably at 50-400 nm, and remelted layer thickness is in 10-40 μ m left and right; Fig. 4 is the sem analysis figure of the continuous Oxide Film Surface Appearance of Fig. 1 floating coat isothermal oxidation 100 h rear interface places formation, illustrates that the thin crystal coating material that this compounding technology is prepared from has good high temperature oxidation resistent susceptibility.
Claims (7)
1. the thin brilliant barrier material of anti-oxidant MCrAlY, comprises superalloy matrix, it is characterized in that, forms MCrAlY protective coating at described superalloy matrix surface, forms Ultra-fine Grained remelted layer on described MCrAlY protective coating surface.
2. the thin brilliant barrier material of the anti-oxidant MCrAlY of one according to claim 1, is characterized in that, described MCrAlY coating adopts air plasma spraying method to obtain, and described Ultra-fine Grained remelted layer adopts high-current pulsed electron beam Technology For Remelting to be prepared from.
3. the thin brilliant barrier material of the anti-oxidant MCrAlY of one according to claim 2, is characterized in that, MCrAlY coating prepared by plasma spraying method, and M is Ni, Co, or the mixture of Ni and Co, coat-thickness is 150-200 μ m.
4. the thin brilliant barrier material of the anti-oxidant MCrAlY of one according to claim 2, it is characterized in that, thin brilliant protective coating prepared by high-current pulsed electron beam Technology For Remelting, coating is smooth surface, densification, equally distributed ultra-fine grained structure, grain-size is 40-500nm.
5. a preparation method for the thin brilliant barrier material of anti-oxidant MCrAlY, is characterized in that, adopts " air plasma spraying+high-current pulsed electron beam " compounding technology, comprises the following steps:
(1) superalloy matrix, after pre-grinding, cleaning, sandblast roughening treatment, utilizes the method for air plasma spraying at superalloy matrix surface deposition MCrAlY protective coating;
(2) the MCrAlY protective coating preparing is carried out to HCPEB bombardment processing, realize MCrAlY coatingsurface remelting processing, complete the preparation of the thin brilliant protective coating of MCrAlY;
(3) the thin crystal coating sample preparing is carried out to high temperature oxidation resistance and detect analysis, detect stopping property and high-temperature oxidation.
6. the preparation method of the thin brilliant barrier material of a kind of anti-oxidant MCrAlY according to claim 5, it is characterized in that, the APS technology adopting in step (1), selection voltage is 37 ~ 39V, electric current is 740 ~ 760A, powder sending quantity is 2 ~ 3rmp, and sandblast speed is 400 ~ 500mm/s, and spray distance is 80 ~ 100mm.
7. the preparation method of the thin brilliant barrier material of a kind of anti-oxidant MCrAlY according to claim 5, is characterized in that, the HCPEB technology adopting in step (2) is selected vacuum tightness P≤8 × 10
-3pa, beam energy is 20 ~ 30KeV, energy density is 4 ~ 10J/cm
2, bombardment number of times is 10 ~ 50 times.
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| CN106435430A (en) * | 2016-12-13 | 2017-02-22 | 江西省科学院应用物理研究所 | Method for anti-oxygenic property of improving thermal spraying MCrAlY coating |
| CN107866631A (en) * | 2016-09-23 | 2018-04-03 | 中国航空工业集团公司北京航空制造工程研究所 | A kind of crystal grain refinement device and method based on the shaping of electron beam fuse |
| CN108103455A (en) * | 2017-12-20 | 2018-06-01 | 江苏大学 | A kind of preparation method of the high-temperature protection coating with novel surface structure |
| CN109763089A (en) * | 2018-12-18 | 2019-05-17 | 江苏大学 | A kind of processing method improving MCrAlY protective coating surface A l content and high-temperature service performance |
| CN110184600A (en) * | 2019-06-20 | 2019-08-30 | 中北大学 | The preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating |
| CN110592592A (en) * | 2019-09-23 | 2019-12-20 | 江苏大学 | Laser cladding high-temperature protective coating surface polishing and purifying method based on pulsed electron beam technology |
| CN111893418A (en) * | 2020-08-08 | 2020-11-06 | 桂林电子科技大学 | Method for improving high-temperature oxidation resistance of nickel-based alloy surface |
| CN114919254A (en) * | 2022-05-27 | 2022-08-19 | 广州方邦电子股份有限公司 | Metal foil, flexible metal-clad plate, semiconductor, negative electrode material, and battery |
| CN115466950A (en) * | 2022-08-11 | 2022-12-13 | 温州大学 | Method for forming heat corrosion resistant coating on surface of substrate |
| CN115747795A (en) * | 2022-12-05 | 2023-03-07 | 江苏大学 | Thermal barrier coating bonding layer with long service life and preparation method thereof |
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| CN107866631A (en) * | 2016-09-23 | 2018-04-03 | 中国航空工业集团公司北京航空制造工程研究所 | A kind of crystal grain refinement device and method based on the shaping of electron beam fuse |
| CN107866631B (en) * | 2016-09-23 | 2020-05-05 | 中国航空制造技术研究院 | Grain refinement device and method based on electron beam fuse forming |
| CN106435430B (en) * | 2016-12-13 | 2019-02-05 | 江西省科学院应用物理研究所 | A method of improving thermal spraying MCrAlY coating antioxygenic property |
| CN106435430A (en) * | 2016-12-13 | 2017-02-22 | 江西省科学院应用物理研究所 | Method for anti-oxygenic property of improving thermal spraying MCrAlY coating |
| CN108103455B (en) * | 2017-12-20 | 2020-06-26 | 江苏大学 | Preparation method of high-temperature protective coating |
| CN108103455A (en) * | 2017-12-20 | 2018-06-01 | 江苏大学 | A kind of preparation method of the high-temperature protection coating with novel surface structure |
| CN109763089A (en) * | 2018-12-18 | 2019-05-17 | 江苏大学 | A kind of processing method improving MCrAlY protective coating surface A l content and high-temperature service performance |
| CN110184600A (en) * | 2019-06-20 | 2019-08-30 | 中北大学 | The preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating |
| CN110592592A (en) * | 2019-09-23 | 2019-12-20 | 江苏大学 | Laser cladding high-temperature protective coating surface polishing and purifying method based on pulsed electron beam technology |
| CN111893418A (en) * | 2020-08-08 | 2020-11-06 | 桂林电子科技大学 | Method for improving high-temperature oxidation resistance of nickel-based alloy surface |
| CN114919254A (en) * | 2022-05-27 | 2022-08-19 | 广州方邦电子股份有限公司 | Metal foil, flexible metal-clad plate, semiconductor, negative electrode material, and battery |
| CN115466950A (en) * | 2022-08-11 | 2022-12-13 | 温州大学 | Method for forming heat corrosion resistant coating on surface of substrate |
| CN115747795A (en) * | 2022-12-05 | 2023-03-07 | 江苏大学 | Thermal barrier coating bonding layer with long service life and preparation method thereof |
| CN115747795B (en) * | 2022-12-05 | 2024-03-26 | 江苏大学 | Thermal barrier coating bonding layer with high service life and preparation method thereof |
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