CN103789715A - Anti-oxidization thermal barrier coating material with long service life and preparation method thereof - Google Patents
Anti-oxidization thermal barrier coating material with long service life and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermal barrier coating surface treatment and modification, and in particular relates to an anti-oxidization thermal barrier coating material with long service life and a preparation method thereof. The coating material comprises a high-temperature alloy substrate, a metal adhesive layer, a fine-grain remelted layer and a ceramic surface layer. The invention also discloses the preparation method of the anti-oxidization thermal barrier coating material with long service life; the preparation method comprises the steps of depositing the metal adhesive layer on the surface layer of the high-temperature alloy substrate by a plasma spraying method after pre-grinding, cleaning and sand-blasting roughening treatment, and then performing remelting treatment on the metal adhesive layer with a high-current pulse electron beam device, performing sand-blasting treatment on the outmost surface layer of the remelted layer, and finally, depositing the ceramic surface layer on the surface layer of the remelted layer by the plasma spraying method. The anti-oxidization thermal barrier coating material with long service life prepared by the preparation method is high in interface bonding force and even in structural constituents, and has stable oxidization resistance and long coating service life in high-temperature service environment.
Description
Technical field
The invention belongs to thermal barrier coating surface treatment and modification technology field, relate in particular to a kind of high life resistance to oxidation heat barrier coat material and preparation method thereof.
Background technology
Along with the fast development of aeronautical and space technology; fuel gas inlet temperature and the efficiency of turbine engine improve constantly; and existing superalloy and cooling technology cannot meet this demand; at present in the world general the most effectively, economic and feasible method is thermal barrier coating (TBCs) material at Workpiece painting with high temperature oxidation and thermal-insulation function; protect the high-temperature components such as blade to avoid the erosion of high-temperature with this; increase combustion turbine power, extend the work-ing life of engine.
A kind of thermal protection system that TBCs is made up of ceramic oxide and the middle layer with high temperature oxidation resistance; The typical aviation of practical application at present mostly adopts bilayer structure with TBCs: play the ceramic topcoats (TC) of heat-blocking action and improve matrix and the metal bonding coating of ceramic layer physical compatibility (BC); The preparation method of thermal barrier coating has multiple, such as laser melting coating, hypersonic flame spraying (HVOF), air plasma spraying (APS), electro beam physics vapour deposition (EB-PVD) etc.; Wherein, air plasma spraying, owing to having higher spray deposited efficiency and bonding strength, low material requirements, the good advantage such as economic benefit, easy technological process, is the main preparation methods of current Civil Aviation Engine thermal barrier coating.
In actual applications, because TBCs is on active service in the severe environment of strong high temperature oxidation and corrosion, and bearing cold cycling frequently impacts, so its work-ing life is very limited, the inefficacy of the form such as coating cracking easily occurs, peel off, come off, and mainly occur on chemical constitution and the metal bonding coating of physicals abrupt change and the bonding interface of ceramic layer; The thermal barrier coating of being prepared by plasma spraying has following shortcoming: coating is loose porous and coated component is inhomogeneous, and surfaceness is larger; Therefore,, in hot environment, extraneous oxygen element, to ceramic layer and metal bonding coating rapid diffusion, forms so-called thermal growth oxide TGO; Because coatingsurface prepared by plasma spraying is loose porous; therefore be difficult to form fine and close continuously TGO protective membrane at coating interface place; and along with further carrying out of oxidizing reaction; Al in transition layer dilution gradually; the element such as Ni, Cr, Co in tack coat can form the macrobead oxide compound with spinel structure; form larger growth stress, and then at coating interface and the inner germinating of TGO layer crackle, finally cause coating premature failure.
Consider in view of above technical problem, the invention discloses a kind of high life resistance to oxidation heat barrier coat material and preparation method thereof; This coated material is mainly divided into three layers: metal bonding coating, thin brilliant remelted layer, ceramic layer; This coated material is introduced one deck remelted layer at ceramic layer and tie-layer interface place, and this remelted layer is carried out to sandblasting, and further the surface structure of alligatoring, can better realize the mechanical bond between ceramic layer and tack coat; In addition, this remelted layer structural constituent is even, there is ultra-fine crystalline structure, in high-temperature oxidation environment, 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 make uncontrolled TGO growth according to the pattern growth of anticipation, and then effectively improve the antioxidant property of coating, be a kind of desirable high life resistance to oxidation heat barrier coat material.
Summary of the invention
In order to solve the technical problem existing in background technology, the present invention proposes a kind of high life resistance to oxidation heat barrier coat material and preparation method thereof; By structure design and preparation method's design; when having solved plasma spray method and preparing coating, tie layer surface is loose porous; interface is difficult to obtain the TGO protective membrane of continuous densification; cause easily cracking, warpage and the problem such as come off of coating; there is stronger high temperature oxidation resistent susceptibility; improve thermo-efficiency, extended work-ing life.
A kind of high life resistance to oxidation heat barrier coat material that the present invention proposes, comprise metallic matrix, form metal bonding coating at described metal base surface, at described metal bonding coating surface formative tissue thin brilliant remelted layer uniformly, form ceramic topcoats on described thin brilliant remelted layer surface.
Described tack coat and ceramic layer all adopt plasma spraying method to obtain, and described thin brilliant remelted layer adopts high-current pulsed electron beam Technology For Remelting to be prepared from.
Described metallic matrix preferably adopts nickel base superalloy, first adopts after sandblast roughening treatment metal refining tack coat again.
Metal bonding coating prepared by described plasma spraying adopts MCrAlY, wherein; M:Co, Ni or Co+Ni, select for routine techniques, and thickness is between 150 ~ 200 μ m.
Thin brilliant remelted layer smooth surface densification prepared by described high-current pulsed electron beam, remelted layer thickness is between 10 ~ 40 μ m.
The top layer of described thin brilliant remelted layer first adopts after sandblast roughening treatment ceramic deposition surface layer again.
It is 6%～8%Y that ceramic topcoats prepared by described plasma spraying preferably adopts quality percentage composition
2o
3stable ZrO
2, thickness is between 200 ~ 300 μ m.
In the present invention, above-mentioned disclosed high life resistance to oxidation heat barrier coat material is compared with existing technology of preparing, have the following advantages: remelting processing is carried out on the metal bonding coating surface that utilizes electron beam microstructure of plasma sprayed method to prepare, coatingsurface forms the remelted layer of even compact, and thickness can reach tens microns; This layer of remelted layer structure refinement, even, can form fast TGO protective membrane in oxidation, thereby effectively suppressed the diffusion of other elements early stage, has improved the antioxidant property of coating, has reduced the generation of cyclic thermal stres, has effectively improved the work-ing life of coating.
The preparation method who the invention allows for a kind of high life resistance to oxidation heat barrier coat material, technical scheme is as follows:
(1), to superalloy matrix, the parts such as such as engine blade, carry out pre-grinding, cleaning, sandblast roughening treatment;
(2) the superalloy matrix surface metal refining tack coat of the method for utilizing plasma spraying after roughening treatment, completes the preparation of metal bonding coating;
(3) metal bonding coating preparing is carried out to pulsed electron beam bombardment processing, realize metal bonding coating surface remelting, complete the preparation of thin brilliant remelted layer;
(4) sandblast roughening treatment is carried out in the top layer of the thin brilliant remelted layer preparing, improve its top layer roughness;
(5) the thin brilliant remelted layer surface deposition ceramic topcoats of the method for utilizing plasma spraying after alligatoring, completes the preparation of thermal barrier coating.
The sand-blast material adopting in described step (1) is 50 ~ 200 order corundum, and sandblast pressure is 0.2 ~ 0.5MPa, and sandblast distance is 100 ~ 150mm.
In described step (2), the plasma spraying technology of employing is, atmospheric plasma spraying technology, and selection voltage is 30 ~ 40V, and electric current is 700 ~ 800A, and spray gun speed is 400 ~ 500mm/s, and spray distance is 70 ~ 100mm.
The HCPEB Technology For Remelting adopting in described step (3), selects vacuum tightness P≤8 × 10
-3pa, beam energy is 20 ~ 40KeV, energy density is 4 ~ 20J/cm
2, bombardment number of times is 5 ~ 50 times, target spacing is from 15 ~ 20cm.
The sand-blast material adopting in described step (4) is 50 ~ 100 order corundum, and pressure is 0.2 ~ 0.5MPa, and sandblast distance is 100 ~ 150mm.
In described step (5), the plasma spraying technology of employing is, atmospheric plasma spraying technology, and selection voltage is 35 ~ 45V, and electric current is 800 ~ 900A, and sandblast speed is 200 ~ 300mm/s, and spray distance is 70 ~ 100mm.
The prepared high life resistance to oxidation heat barrier coat material of the present invention has uniform coating interface, has strengthened interface binding power, has effectively controlled formation and the growth of TGO, has alleviated interfacial stress, has effectively improved work-ing life and the antioxidant property of coating.
Accompanying drawing explanation
Fig. 1 is a kind of high life resistance to oxidation heat barrier coat material cross section scanning electron microscope (SEM) figure in the present invention;
Fig. 2 is section S EM figure after heat barrier coat material isothermal oxidation 200h in Fig. 1.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
(1) preparation of thermal barrier coating:
S1, superalloy matrix is carried out to pre-grinding, cleaning, sandblast roughening treatment; Selecting sand-blast material according to the technical requirements of sand-blast device is 60 order white fused aluminas, and pressure is 0.4MPa, and sandblast distance is 120mm.
S2, the superalloy matrix surface metal refining tack coat Co23Cr13Al0.5Y of method after roughening treatment that utilizes air plasma spraying, complete the preparation of metal bonding coating, and adhesive layer thickness is 160 μ m; According to air plasma spraying equipment requirements, selecting voltage is 38V, and electric current is 750A, and spray gun speed is 450mm/s, and spray distance is 85mm.
S3, the metal bonding coating preparing is carried out to HCPEB bombardment processing, complete the preparation of thin brilliant remelted layer; Selecting beam energy according to the technical requirements of HCPEB equipment is 27KeV, and energy density is 4J/cm
2, target spacing, from being 15cm, carries out radiation treatment 10,20 and 30 times to sample.
S4, sandblast roughening treatment is carried out in the top layer of the thin brilliant remelted layer preparing, improve its top layer roughness; Selecting sand-blast material according to the technical requirements of sand-blast device is 60 order white fused aluminas, and sandblast pressure is 0.3MPa, and sandblast distance is 120mm.
S5, remelted layer surface deposition 8% Y of method after alligatoring that utilizes air plasma spraying
2o
3stable ZrO
2ceramic topcoats, completes the preparation of thermal barrier coating, and ceramic topcoats thickness is at 240 μ m; According to air plasma spraying equipment requirements, selection voltage is 39V, and electric current is 860A, and spray gun speed is 250mm/s, and spray distance is 72mm.
(2) high temperature oxidation resistance test
S6, the thermal barrier coating preparing is placed in the box heat treatment furnace of sealing, in normal pressure still air atmosphere 1050
oisothermal oxidation 200h under C.
(3) thermal circulation performance test
S7, the thermal barrier coating preparing is placed in the box heat treatment furnace of sealing, in normal pressure still air atmosphere 1050
oafter being incubated 20min under C, take out, utilize pressure-air cooling 10min, this process is designated as a thermal cycling, remembers altogether 200 thermal cyclings.
SEM observation is carried out in thermal barrier coating cross section.Result demonstration, after different pulse number bombardment processings, interface remelted layer thickness thickens with the increase of bombardment number of times, and remelted layer is combined intact with ceramic layer interface, occur without microdefects such as hole crackles.
Can test thermal barrier coating high temperature oxygen endurance.Static oxidization demonstration at 1050 ℃, in ceramic layer and remelted layer interface, TGO is continuous, an even and fine and close oxide film structure, only has a small amount of Cr, Co oxide compound to occur, and along with the increase TGO thickness of bombardment number of times constantly reduces.
Thermal cycling performance of thermal barrel coating is tested; In view of at present thermal shock resistance not yet being had to unified evaluation index, present case contrasts the most frequently used Double-layer Thermal Barrier Coatings and judges the raising of this case coating thermal shock performance, and experimental result shows, after 200 thermal cyclings, original duplex coating surface film oxide comes off and exceedes 20%, and declaration was lost efficacy; Three layers of coatingsurface oxide film that present case proposes only have small part to come off, and it is excellent that after the coating shedding area of preparing after 10 bombardments is no more than and bombards for 10%, 20 time, the coating shedding area of preparation is no more than the rear thermal barrier coating surface of preparing of 5%, 30 bombardment.
embodiment 2
With embodiment 1, only change electron beam parameter in step S3, selecting beam energy according to the technical requirements of HCPEB equipment is 21.6,23.4 and 27KeV, energy density is 4J/cm
2, metal bonding coating is carried out to radiation treatment 30 times.
SEM observation is carried out in thermal barrier coating cross section.Result demonstration, after different pulse energy bombardment processings, interface remelted layer thickness thickens with the increase of bombarding energy, and remelted layer is combined intact with ceramic layer interface, occur without microdefects such as hole crackles.
Can test thermal barrier coating high temperature oxygen endurance.Static oxidization demonstration at 1050 ℃, in ceramic layer and remelted layer interface, TGO is a continuous uniform and fine and close oxide film structure, and along with the increase TGO thickness of bombarding energy constantly reduces.
The high thermal circulation performance of thermal barrier coating is tested.Experimental result demonstration, after 200 thermal cyclings, original duplex coating surface film oxide comes off and exceedes 20%, and declaration was lost efficacy; Three layers of coatingsurface oxide film that present case proposes only have small part to come off, and thermal barrier coating prepared by low-yield 21.6KeV and the middle energy 23.4KeV area that comes off is no more than 5%, and thermal barrier coating surface prepared by high-energy 27KeV stands intact.
embodiment 3
With embodiment 1, only change the composition of metal bonding coating in step S2, the superalloy matrix surface metal refining tack coat Ni21Co32Cr8Al0.5Y of the method for utilizing air plasma spraying after roughening treatment, completes the preparation of metal bonding coating.
SEM observation is carried out in thermal barrier coating cross section.Result demonstration, after different pulse number bombardment processings, interface remelted layer thickness thickens with the increase of bombardment number of times, and remelted layer is combined intact with ceramic layer interface, occur without microdefects such as hole crackles.
Can test thermal barrier coating high temperature oxygen endurance.Static oxidization at 1050 ℃ shows, in ceramic layer and remelted layer interface, TGO is a continuous uniform and fine and close oxide film structure, only has a small amount of Ni, Cr, Co mixed oxide to occur, and along with the increase TGO thickness of bombardment number of times constantly reduces.
The high thermal circulation performance of thermal barrier coating is tested.Experimental result demonstration, after 200 thermal cyclings, original duplex coating surface film oxide comes off and exceedes 20%, and declaration was lost efficacy; Three layers of coatingsurface oxide film that present case proposes only have small part to come off, and the area that comes off after 10 times and 20 bombardment processings is no more than 5%, and the thermal barrier coating surface of 30 bombardment preparations of electron beam stands intact.
embodiment 4
With embodiment 1, only change the composition of metal bonding coating in step S2, the superalloy matrix surface metal refining tack coat Ni21Co32Cr8Al0.5Y of the method for utilizing air plasma spraying after roughening treatment, completes the preparation of metal bonding coating.
SEM observation is carried out in thermal barrier coating cross section; Result demonstration, after different pulse number bombardment processings, interface remelted layer thickness thickens with the increase of bombardment number of times, and remelted layer is combined intact with ceramic layer interface, occur without microdefects such as hole crackles.
Can test thermal barrier coating high temperature oxygen endurance; Static oxidization demonstration at 1050 ℃, in ceramic layer and remelted layer interface, TGO is a continuous uniform and fine and close oxide film structure, and along with the increase TGO thickness of bombardment number of times constantly reduces.
The high thermal circulation performance of thermal barrier coating is tested; Experimental result demonstration, after 200 thermal cyclings, original duplex coating surface film oxide comes off and exceedes 20%, and declaration was lost efficacy; Three layers of coatingsurface oxide film that present case proposes only have small part to come off, and thermal barrier coating prepared by low-yield 21.6KeV and the middle energy 23.4KeV area that comes off is no more than 5%, and thermal barrier coating surface prepared by high-energy 27KeV stands intact.
The heat barrier coat material obtaining in embodiment 1-4 has three-decker, is respectively ceramic layer, thin brilliant remelted layer, metal bonding coating, and its Cross Section Morphology as shown in Figure 1; Fig. 1 is high life resistance to oxidation thermal barrier coating section S EM analysis chart; Fig. 2 is section S EM figure after heat barrier coat material isothermal oxidation 200h in Fig. 1; Result demonstration, the thermal barrier coating interface that this compounding technology is prepared from is in conjunction with being improved significantly, and thin brilliant remelted layer thickness is between 10-40 μ m, and it is beneficial to formation and the growth of TGO.This thermal barrier coating has good high temperature oxidation resistent susceptibility and longer work-ing life.
Claims (11)
1. a high life resistance to oxidation heat barrier coat material, comprise superalloy matrix, it is characterized in that, form metal bonding coating at described superalloy matrix surface, at described metal bonding coating surface formative tissue thin brilliant remelted layer uniformly, form ceramic topcoats on described thin brilliant remelted layer surface.
2. a kind of high life resistance to oxidation heat barrier coat material according to claim 1, it is characterized in that: described metal bonding coating and ceramic layer all adopt plasma spraying method to obtain, described thin brilliant remelted layer adopts high-current pulsed electron beam Technology For Remelting to be prepared from.
3. a kind of high life resistance to oxidation heat barrier coat material according to claim 2, is characterized in that: metal bonding coating prepared by described plasma spraying adopts MCrAlY, and M is Co, Ni or Co+Ni, and coat-thickness is between 150-200 μ m.
4. a kind of high life resistance to oxidation heat barrier coat material according to claim 2, is characterized in that: thin brilliant remelted layer thickness prepared by high-current pulsed electron beam is between 10-40 μ m.
5. a kind of high life resistance to oxidation heat barrier coat material according to claim 2, is characterized in that: it is 6%～8%Y that ceramic topcoats prepared by plasma spraying adopts quality percentage composition
2o
3stable ZrO
2, thickness is between 200-300 μ m.
6. a preparation method for high life resistance to oxidation heat barrier coat material, is characterized in that:: comprise the steps:
(1) superalloy matrix is carried out to pre-grinding, cleaning, sandblast roughening treatment;
(2) the superalloy matrix surface metal refining tack coat of the method for utilizing plasma spraying after roughening treatment, completes the preparation of metal bonding coating;
(3) metal bonding coating preparing is carried out to HCPEB bombardment processing, realize metal bonding coating surface remelting, complete the preparation of thin brilliant remelted layer;
(4) sandblast roughening treatment is carried out in the top layer of the thin brilliant remelted layer preparing, improve its top layer roughness;
(5) the thin brilliant remelted layer surface deposition ceramic topcoats of the method for utilizing plasma spraying after alligatoring, completes the preparation of thermal barrier coating.
7. the preparation method of a kind of high life resistance to oxidation heat barrier coat material according to claim 6, is characterized in that, the sand-blast material adopting in described step (1) is 50 ~ 200 order corundum, and pressure is 0.2 ~ 0.5MPa, and sandblast distance is 100 ~ 150mm.
8. the preparation method of a kind of high life resistance to oxidation heat barrier coat material according to claim 6, it is characterized in that, the plasma spraying technology adopting in described step (2) is atmospheric plasma spraying technology, selection voltage is 30 ~ 40V, electric current is 700 ~ 800A, spray gun speed is 400 ~ 500mm/s, and spray distance is 70 ~ 100mm.
9. the preparation method of a kind of high life resistance to oxidation heat barrier coat material according to claim 6, is characterized in that, the HCPEB Technology For Remelting adopting in described step (3) is selected vacuum tightness P≤8 × 10
-3pa, beam energy is 20 ~ 40KeV, energy density is 4 ~ 20J/cm
2, bombardment number of times is 5 ~ 50 times, target spacing is from being 15 ~ 20cm.
10. the preparation method of a kind of high life resistance to oxidation heat barrier coat material according to claim 6, is characterized in that, the sand-blast material adopting in described step (4) is 50 ~ 100 order corundum, and pressure is 0.2 ~ 0.5MPa, and sandblast distance is 100 ~ 150mm.
The preparation method of 11. a kind of high life resistance to oxidation heat barrier coat materials according to claim 6, it is characterized in that, the plasma spraying technology adopting in described step (5) is atmospheric plasma spraying technology, selection voltage is 35 ~ 45V, electric current is 800 ~ 900A, spray gun speed is 200 ~ 300mm/s, and spray distance is 70 ~ 100mm.
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| CN114150254A (en) * | 2021-11-10 | 2022-03-08 | 中国科学院上海硅酸盐研究所 | Thermal barrier coating for TiAl alloy and preparation method thereof |
| CN114150254B (en) * | 2021-11-10 | 2022-09-06 | 中国科学院上海硅酸盐研究所 | Thermal barrier coating for TiAl alloy and preparation method thereof |
| CN115418599A (en) * | 2022-08-24 | 2022-12-02 | 昆山西诺巴精密模具有限公司 | Thermal barrier coating of engine impeller and surface treatment method |
| CN115627438A (en) * | 2022-10-31 | 2023-01-20 | 西安交通大学 | Method for improving oxidation resistance of metal bonding layer of thermal barrier coating |
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