CN115747795B - Thermal barrier coating bonding layer with high service life and preparation method thereof - Google Patents
Thermal barrier coating bonding layer with high service life and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
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Abstract
The invention discloses a thermal barrier coating bonding layer with a high service life and a preparation method thereof. The invention regulates the distribution form of rare earth elements in the bonding layer by a strong current pulse electron beam technology with short pulse width, low energy and multiple times of irradiation, so that rare earth elements form rare earth enriched nano-dispersion particles, thereby obtaining the bonding layer with the rare earth elements uniformly distributed in the enriched nano-particle form, overcoming the defect of unfavorable oxidation resistance caused by uneven distribution of the rare earth elements in the bonding layer or easy agglomeration in the oxide form, and having important significance for improving the high-temperature oxidation resistance of the thermal barrier coating.
Description
Technical Field
The invention belongs to the technical field of surface modification, and particularly relates to a thermal barrier coating bonding layer with a long service life and a preparation method thereof.
Background
Thermal barrier coatings (Thermal Barrier Coating, TBC) are widely used in aircraft engines and gas turbines for their high thermal insulation, oxidation resistance, and the like. Conventional TBCs are bilayer structures consisting of a top ceramic layer and a bottom MCrAlY (M is Ni, co or Ni+Co) tie layer. Under high temperature conditions, a thermally grown oxide layer (TGO) forms at the MCrAlY interface, which is a key factor affecting the thermodynamic performance and durability of TBC. The ideal TGO is composed of continuous, dense and slow-growing alpha-Al 2 O 3 It is constructed with shielding ability against element diffusion, good adhesion and less volume change at transition. However, under severe service environment, ideal Al 2 O 3 It is difficult to stably grow, and as oxidation time continues and thermal stress continues to accumulate, the accumulation of stress in the oxide film causes changes in the morphology and composition of TGO, and gradually cracks and peels, eventually leading to failure of the coating.
At present, the thermal spraying technology for preparing the bonding layer is most widely applied to aeroengines. The thermal spraying technology mainly comprises Low Pressure Plasma Spraying (LPPS) and supersonic flame spraying (HVOF), the bonding layers prepared by the two technologies have higher compactness and better high-temperature oxidation resistance, but the bonding layer surfaces prepared by the two technologies have higher surface roughness, and the prepared bonding layer components cannot realize complete homogenization distribution.
In order to further improve the high-temperature oxidation resistance of the bonding layer, researchers begin to develop six-membered and seven-membered bonding layers, namely, the bonding layers mainly comprise trace rare earth active elements. In the bonding layer, the rare earth element plays a very important role, wherein the rare earth element represented by Y can improve the adhesion of TGO and reduce the growth rate of TGO, so that the high-temperature oxidation resistance and the hot corrosion resistance of the bonding layer are improved. In addition, ta, si, hf and other elements are added to promote Al 2 O 3 Nucleation rate and improved adhesion. However, for the bonding layer, the distribution of the doped rare earth elements is not controllableIf the rare earth element is excessively added, a segregation phenomenon can also occur; and because rare earth elements have strong oxygen affinity, the rare earth elements exist in the form of oxides, if the service temperature is too high or the heat preservation time is too long, complex oxides are easy to further form, and once the oxides are aggregated, the 'rare earth element effect' is lost, so that an oxide film grows rapidly, and the deterioration effect on a bonding layer is realized.
Application publication No. CN108396278A discloses a long-life MCrAlY coating, a preparation method and application thereof in hot end parts, which adopts a diffusion Y technique to prepare the long-life MCrAlY coating, wherein Y in the coating is a high-stability intermetallic compound M 5 Form Y, which can exist through M 5 Y realizes stable supply of Y in the coating, avoids rapid oxidation of Y, further improves the thermal stability of the coating and prolongs the service life of the coating. Although the method changes the existence form of the Y element of the original coating, the distribution of the Y element is very uneven and is not controllable in microstructure.
Application publication No. CN102719782A discloses a treatment method for improving oxidation resistance of thermal barrier coating adhesive layer, which adopts 50-200 mu s long pulse width and 8-18J/cm 2 The MCrAlY bonding layer is sprayed by high-energy-density electron beam irradiation plasma, so that the surface roughness of the coating is reduced, the pores and holes of the coating are reduced, and the oxidation resistance of the coating is effectively improved. However, the technology only reduces the surface roughness of the coating and forms a compact melting layer, and has a certain effect on improving the oxidation resistance of the coating, but the modification effect is limited, and no mention is made of the fine crystal effect and the element regulation effect due to the large pulse width and the long remelting time. For the MCrAlY series bonding layer, the higher the service temperature is, the more serious the element diffusion is, and the defect that rare earth elements are aggregated and form oxides, so that the high-temperature oxidation resistance of the bonding layer is reduced still exists.
Disclosure of Invention
Based on the technical problems, the invention provides the thermal barrier coating bonding layer with high service life and the preparation method thereof, and the distribution form of rare earth elements in the bonding layer is regulated and controlled by a strong-current pulse electron beam technology with short pulse width, low energy and multiple times of irradiation, so that rare earth elements form rare earth enriched nano-dispersion particles, and the bonding layer with the rare earth elements uniformly distributed in the enriched nano-particle form is obtained, thereby overcoming the defect of unfavorable oxidation resistance caused by uneven distribution of the rare earth elements in the bonding layer or easy agglomeration in the oxide form, and having important significance for improving the high-temperature oxidation resistance of the thermal barrier coating.
The invention provides a thermal barrier coating bonding layer with a high service life, which is an MCrAlY or MCrAlYX bonding layer, wherein rare earth elements in the bonding layer are uniformly distributed in the form of enriched nano particles.
The rare earth element in the bonding layer forms Al-Y enriched nano particles which are uniformly distributed in the coating and can be used as Al 2 O 3 Effectively promote the rapid formation of oxide films and anchor Al through dispersed nano' oxide pins 2 O 3 The folds of the oxide film are reduced, the growth rate of the oxide is slowed down, local rapid oxidation of rare earth elements such as Y is avoided, the thermal stability of the bonding layer is effectively improved, and the high service life of the thermal barrier coating is prolonged.
Preferably, in the MCrAlY or MCrAlYX bonding layer, M is one of Ni or Co, and X is at least one of Ta, si, hf, zr; preferably, X is Ta.
When X in the MCrAlYX bonding layer is Ta, the active element effect can be exerted, and Ta elements are uniformly distributed in the form of enriched nano particles, so that the bonding layer with more excellent performance is obtained.
Preferably, the content of Y in the MCrAlY or MCrAlYX bonding layer is at least 0.8wt%.
Preferably, the enriched nanoparticles are Y-Al enriched nanoparticles.
The invention also provides a preparation method of the thermal barrier coating bonding layer with the high service life, which comprises the following steps: after preparing an MCrAlY or MCrAlYX bonding layer on the surface of a substrate, carrying out irradiation treatment on the MCrAlY or MCrAlYX bonding layer by adopting a pulse electron beam process, and eliminating the defect of uneven element distribution in the MCrAlY or MCrAlYX bonding layer, so that rare earth elements in the bonding layer are uniformly distributed in the form of enriched nano particles, and the thermal barrier coating bonding layer with the high service life is obtained.
In the invention, remelting can occur on the surface of the MCrAlY or MCrAlYX bonding layer after the irradiation of the high-current pulse electron beam, so that the defects of surface roughness, microcracks and the like generated in the original bonding layer preparation process can be obviously eliminated, the surface roughness is reduced, planarization is realized, the formation of flat and consistent-thickness TGO during high-temperature oxidation is facilitated, and the stress concentration area is eliminated; at the microscopic level, the remelting effect induced by the irradiation of the intense pulsed electron beam can cause the surface area to be in a modified state similar to quenching, rapid remelting and cooling process (10 7-9 K/s) initiates the massive formation of nanocrystals, and the accompanying stress also creates abundant microscopic defects, which provide a channel for the selective diffusion of Al elements during the oxidation phase; more importantly, the unbalanced solidification process initiated by electron beam irradiation in the remelting process can realize the regulation and control of the distribution and the existence form of the rare earth elements, and the regulation and control is specifically shown as follows: after the low-frequency electron beam irradiation modification, the energy injection of the electron beam causes remelting vaporization on the surface of the bonding layer, rare earth elements and aluminum elements in vaporization components are oxidized at a lower vacuum degree due to high temperature and high activity, and finally, the rare earth elements and the aluminum elements are redeposited on the surface of the coating in the form of rare earth-aluminum oxide particles, and the redeposited particles obviously improve the rare earth element content on the surface of the coating; after electron beam irradiation modification under high times, re-deposited particles are remelted repeatedly and separated out in a rapid cooling process to form rare earth enriched nano-dispersed particles densely distributed in a remelting layer, so that the rare earth elements are uniformly diffused in depth; the obtained rare earth enriched nanoparticle structure can effectively promote the rapid formation of compact TGO in the initial oxidation stage, form rare earth oxide nails in the subsequent oxidation stage, remarkably improve the TGO binding force, reduce the growth rate of the TGO, enable the obtained binding layer to have excellent high-temperature oxidation resistance, and meet the actual application requirements of the thermal barrier coating of the aeroengine.
According to the invention, through a high-temperature oxidation resistance experiment and a thermal cycle experiment, the rare earth enriched nano-dispersion particles which are regulated and controlled on the surface of the bonding layer by utilizing the pulse electron beam can be effectively obtainedPromote the rapid formation of a continuous and compact Al layer at the coating interface in the initial oxidation stage 2 O 3 The protective film and the Y oxide pins with extremely small size are uniformly distributed in the oxide film, so that the adhesion of the oxide film is greatly improved, and the high-temperature oxidation resistance and the hot corrosion resistance of the coating at 1100 ℃ and 1150 ℃ are improved by more than two times.
Preferably, the MCrAlY or MCrAlYX bonding layer is prepared on the surface of the substrate by adopting a low-pressure plasma spraying process.
The pulsed electron beam technology is a self-quenching technology, which can realize heating and melting, even vaporization, of a material surface layer, then quickly cool and solidify by means of heat conduction of the material, and induce a series of physicochemical processes, and as the temperature gradient induced by irradiation is extremely large, the processes belong to typical unsteady processes, and many special metastable structures are induced to form, but the modification effects of the materials for different bonding layers are greatly different: the surface of the bonding layer prepared by the atmospheric plasma spraying technology has too many pores and many oxide inclusions, and the surface polishing effect is difficult to realize and the Y enriched nano-dispersion particles are difficult to induce to form on the surface of the coating due to the overflow of internal gas and the oxide quality control effect in the irradiation process; the bonding layer prepared by the low-pressure plasma spraying technology is relatively compact, and the modification effect in the invention can be realized by reasonably controlling the coordination of multiple processes in the irradiation process;
preferably, the MCrAlY or MCrAlYX bonding layer is subjected to multiple irradiation treatments under vacuum conditions by adopting a pulse electron beam process with short pulse width, low energy and multiple times.
Firstly, starting from regulating and controlling the energy density and pulse width parameters of a pulse electron beam, the energy density and the pulse width are required to be controlled to be coordinated, if irradiation treatment is carried out by adopting higher energy density and long pulse width, the vaporization phenomenon on the surface of a bonding layer is aggravated, the consumption of Al element is caused, and the solidification effect reaches the effect of uniform precipitation of non-nano particles; secondly, starting from regulating and controlling the irradiation times of the pulsed electron beam, the method is important to regulating and controlling rare earth enriched nano-dispersion particles: because the surface roughness of the bonding layer is larger, under low-frequency irradiation, the bonding layer in the higher convex area is firstly discharged and vaporized to form some vaporized particles to be redeposited on the surface of the bonding layer, but the surface of the bonding layer is not thoroughly melted; with the increase of irradiation times, the bonding layer is continuously subjected to the accumulation process of melting-solidification, the surface is continuously polished, and some vaporization particles formed before are also continuously melted into a liquid solution for redistribution, and the Y element is easy to separate out to form nano dispersion particles due to lower solid solubility in a matrix; however, once the irradiation times are too high, the surface vaporization phenomenon of the coating layer is aggravated again due to the heat accumulation effect, the surface of the bonding layer starts to have a relief appearance, and the nano-dispersed particles gradually disappear.
Therefore, in the present invention, it is necessary to reasonably control the irradiation parameters of the pulsed electron beam: according to the research, the bonding layer is treated by adopting low-energy, short-pulse width and multiple times of irradiation, the surface of the bonding layer has the most uniform Y enriched nano-dispersed particles, and other rare earth elements are uniformly distributed in a coating matrix; rare earth enriched nano-dispersion particles formed on the surface of the coating by induction under the action of pulse electron beams can effectively improve the protective oxide film Al in the initial stage of oxidation 2 O 3 The nucleation rate of the rare earth element is promoted, the rapid formation of the rare earth element is promoted, the steady-state growth of the surface of the coating is realized by means of electron beam polishing, the rare earth element can form an oxide nail with extremely small size in the later oxidation stage, the adhesiveness of an oxide film is effectively pinned, the growth rate of the oxide film is reduced, the obtained bonding layer has extremely excellent high-temperature oxidation resistance and hot corrosion resistance, and the requirements of the actual application of the thermal barrier coating of the aeroengine are met.
Preferably, the pulse width is 1-3 μs, the electron beam energy is 20-30keV, and the energy density is 3-10J/cm 2 The irradiation times are 5-40 times.
Preferably, the pulse width is 1.5 μs, the electron beam energy is 27keV, and the energy density is 5-8J/cm 2 The irradiation times are 20-30 times.
The invention provides a thermal barrier coating bonding layer with high service life and a preparation method thereof, and particularly relates to a preparation method of an MCrAlY or MCrAlYX bonding layer on the surface of a substrate by utilizing a low-pressure plasma process, and then the MCrAlY or MCrAlYX bonding layer is subjected to multiple irradiation treatment by utilizing a short pulse width and low energy pulse electron beam technology, so that rough defects on the surface of the bonding layer are eliminated, a polished surface is formed, surface layer grains are thinned, uneven element distribution in the bonding coating is eliminated, and the rare earth elements are controlled to be uniformly distributed in the form of nano particles. The rare earth element enriched nano-dispersed particles formed in the bonding layer are uniformly distributed, so that the nucleation rate of the protective oxide film can be greatly improved, the adhesiveness of the protective oxide film is effectively improved, and the high-temperature oxidation resistance and hot corrosion resistance of the coating are improved by more than two times.
Aiming at the defects of the high-temperature protective coating in the prior art, the invention starts from a modification process and utilizes a strong-current pulse electron beam irradiation process to regulate the distribution form of rare earth elements in the MCrAlY or MCrAlYX bonding layer, thereby improving the service performance of the thermal barrier coating, not only eliminating the surface defects of the bonding layer, but also effectively regulating the distribution form of the added elements near the surface layer of the bonding coating, in particular obtaining Y element enriched nano-dispersion particles, and having very important significance for improving the high-temperature oxidation resistance of the bonding layer.
Drawings
FIG. 1 is a topography of an original NiCrAlY bonding layer according to example 1-2 of the present invention;
FIG. 2 is a TEM morphology and active element Y distribution diagram of the original NiCrAlY bonding layer of example 1-2 of the present invention;
FIG. 3 is a graph showing the 5J/cm ratio of example 2 of the present invention 2 Electron beam energy density irradiation modified TEM morphology and active element Y distribution diagram of NiCrAlY bonding layer;
FIG. 4 is a graph showing the morphology of an oxide film after high temperature oxidation of an original NiCoCrAlYTA bond coat in example 3 of the present invention;
FIG. 5 is a graph showing the morphology of an oxidized film after high temperature oxidation of an irradiation-modified NiCoCrAlYTA adhesive layer according to example 3 of the present invention.
Detailed Description
The present invention will be described in detail by way of specific examples, which should be clearly set forth for the purpose of illustration and are not to be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a preparation method of a thermal barrier coating bonding layer with high service life, which comprises the following steps:
(1) Grinding and polishing the surface of the superalloy substrate, ultrasonically cleaning the superalloy substrate with acetone and alcohol to remove greasy dirt, and then performing sand blasting treatment to obtain a pretreated superalloy substrate;
(2) Preparing an original NiCrAlY bonding layer on the surface of the pretreated high-temperature alloy substrate by adopting a low-pressure plasma spraying process, and selecting spraying parameters according to the preparation requirements of the bonding layer: the current is 1700A, the voltage is 55V, the power is 86kw, the powder feeding speed is 35g/min, and the spray distance is 500mm;
(3) Under the vacuum condition, the original NiCrAlY bonding layer is irradiated by adopting a pulsed electron beam process, and irradiation parameters are selected according to irradiation modification requirements of the bonding layer: vacuum degree P is less than or equal to 5 multiplied by 10 -3 Pa, electron beam energy of 27KeV, pulse width of 1.5 μs, and energy density of 5J/cm 2 The bombardment times are 10, 20, 30 and 40 times, and the modified NiCrAlY bonding layer is obtained by irradiation for different times, namely the thermal barrier coating bonding layer with long service life.
Observing the original NiCrAlY bonding layer by adopting a three-dimensional confocal microscope to obtain a morphology diagram of the original NiCrAlY bonding layer, which is shown in FIG. 1 and is described in the embodiment 1 of the invention; referring to FIG. 1, it can be seen that the original NiCrAlY adhesive layer has a surface roughness as high as 8 μm, while the modified NiCrAlY adhesive layer is irradiated for different times to greatly reduce the surface roughness, which is respectively 3.5 μm (10 times), 2.0 μm (20 times), 1.3 μm (30 times) and 2.9 μm (40 times);
observing the original NiCrAlY bonding layer and the different times of irradiation modified NiCrAlY bonding layers by adopting a scanning electron beam microscope, the surface of the original NiCrAlY bonding layer is rough and uneven, more unmelted large particles exist, and in the different times of irradiation modified NiCrAlY bonding layers, the surface of the 10 times of irradiation modified bonding layers is not thoroughly melted, the surface of the 20 times of irradiation modified bonding layers and the 30 times of irradiation modified bonding layers is thoroughly melted, the polishing effect is good, obvious nano crystal grains can be observed on the surface, the surface of the 40 times of irradiation modified bonding layers has a fluctuation shape, and more vaporization particles are deposited on the surface; it shows that under the low-frequency irradiation, the surface of the bonding layer is not thoroughly melted, and as the irradiation frequency increases, the surface of the bonding layer is continuously polished and smoothed, but when the irradiation frequency is too high, the surface vaporization is aggravated, and the phenomenon of Al element damage occurs.
And carrying out detailed analysis on the original NiCrAlY bonding layer and the surface molten layer of the modified NiCrAlY bonding layer subjected to different times of irradiation by using a transmission electron microscope to obtain a TEM morphology and an active element Y distribution diagram of the original NiCrAlY bonding layer in the embodiment 1 of the invention shown in figure 2. As shown in fig. 2, the element distribution inside the original NiCrAlY bonding layer is very uneven; in the NiCrAlY bonding layer modified by irradiation for different times, the nano particles in the 10 times of irradiation modification bonding layer are not obvious, the nano particles can be formed by 20 times of irradiation modification bonding layer and 30 times of irradiation modification bonding layer, the size of the nano particles is gradually reduced along with the increase of the irradiation times, and the number of the nano particles on the surface of the 40 times of irradiation modification bonding layer is reduced;
then respectively testing the oxidation resistance of the original NiCrAlY bonding layer and the irradiation modified NiCrAlY bonding layer with different times at 1150 ℃, and the result shows that the surface of the original NiCrAlY bonding layer can form continuous Al in the initial stage of oxidation 2 O 3 An oxide film, but a small amount of mixed oxide is doped in the oxide film, and the phenomenon of wrinkling of the oxide film is serious; the surface of the NiCrAlY bonding layer can be modified by irradiation for different times to form a layer of continuous and compact Al 2 O 3 A protective film; in the later oxidation period, the original oxide film of the NiCrAlY bonding layer has serious peeling, serious internal oxidation and invalid coating; the oxide film on the surface of the NiCrAlY bonding layer is still continuous and compact after different times of irradiation modification, wherein the mixed oxide content in the oxide film of the NiCrAlY bonding layer is higher after 10 times of irradiation modification, a small amount of internal oxidation locally occurs, the oxide film of the NiCrAlY bonding layer is the most compact after 20 times of irradiation modification and 30 times of irradiation modification, the phenomena of internal oxidation and oxide film peeling are not seen, the thickness of the oxide film on the surface of the NiCrAlY bonding layer is the thinnest after 30 times of irradiation modification, and the oxide film of the NiCrAlY bonding layer locally occurs small-area peeling after 40 times of irradiation modification; in contrast, 30 times of irradiation modified bonding layers have optimal oxidation resistance, and the oxidation resistance of the bonding layers is improved by more than 2 times.
Example 2
The embodiment provides a preparation method of a thermal barrier coating bonding layer with high service life, which comprises the following steps:
(1) Grinding and polishing the surface of the superalloy substrate, ultrasonically cleaning the superalloy substrate with acetone and alcohol to remove greasy dirt, and then performing sand blasting treatment to obtain a pretreated superalloy substrate;
(2) Preparing an original NiCrAlY bonding layer on the surface of the pretreated high-temperature alloy substrate by adopting a low-pressure plasma spraying process, and selecting spraying parameters according to the preparation requirements of the bonding layer: the current is 1700A, the voltage is 55V, the power is 86kw, the powder feeding speed is 35g/min, and the spray distance is 500mm;
(3) Under the vacuum condition, the original NiCrAlY bonding layer is irradiated by adopting a pulsed electron beam process, and irradiation parameters are selected according to irradiation modification requirements of the bonding layer: vacuum degree P is less than or equal to 5 multiplied by 10 -3 Pa, electron beam energy of 27KeV, pulse width of 1.5 μs, bombardment times of 24 times, and energy densities of 3, 5, 8, and 10J/cm respectively 2 Obtaining modified NiCrAlY bonding layers with different electron beam energy densities through irradiation, namely the thermal barrier coating bonding layers with the high service life;
observing the original NiCrAlY bonding layer by adopting a three-dimensional confocal microscope to obtain a morphology diagram of the original NiCrAlY bonding layer in the embodiment 2 of the invention shown in figure 1; as can be seen from FIG. 1, the original NiCrAlY adhesive layer has a surface roughness as high as 8 μm, while the modified NiCrAlY adhesive layer is greatly reduced by irradiation with electron beams of different energy densities, respectively 2.4 μm (3J/cm) 2 )、2.0μm(5J/cm 2 )、1.6μm(8J/cm 2 )、2.8μm(10J/cm 2 )；
The original NiCrAlY bonding layer and the modified NiCrAlY bonding layer subjected to electron beam irradiation with different energy densities are observed by adopting a scanning electron beam microscope, so that the surface of the original NiCrAlY bonding layer is rough and uneven, more unmelted large particles exist, and 3J/cm of the modified NiCrAlY bonding layer subjected to electron beam irradiation with different energy densities 2 Energy density electron beam irradiation modified adhesive layer surface is not thoroughly melted, 5J/cm 2 And 8J/cm 2 (Energy)The surface of the density electron beam irradiation modified bonding layer is thoroughly melted, the polishing effect is good, obvious nano grains can be observed on the surface, and the density electron beam irradiation modified bonding layer is 10J/cm 2 The energy density electron beam irradiation modified bonding layer surface is thoroughly melted, but more vaporization deposition particles exist on the surface layer, and the surface layer is fluctuant; description of 3J/cm 2 The energy density is too low, the surface of the coating is not thoroughly melted, and the energy density is 10J/cm 2 The energy density is too high, and obvious vaporization phenomenon appears on the surface of the bonding layer;
the original NiCrAlY bonding layer and the molten layer on the surface layer of the modified NiCrAlY bonding layer irradiated by different electron beam energy densities are analyzed in detail by a transmission electron microscope to obtain the TEM morphology and the active Y element distribution diagram of the original NiCrAlY bonding layer in the embodiment 2 of the invention shown in FIG. 2 and the 5J/cm distribution diagram in the embodiment 2 of the invention shown in FIG. 3 2 Electron beam energy density irradiation modified TEM morphology and active element Y distribution diagram of NiCrAlY bonding layer; referring to FIG. 2, the original NiCrAlY bonding layer has very uneven distribution of elements therein, and no obvious Y enriched particles are seen; referring to FIG. 3, it can be seen that in the modified NiCrAlY adhesive layer by electron beam irradiation with different energy densities, 3J/cm 2 The nano particles in the energy density electron beam irradiation modified bonding layer are not obvious, and the energy density electron beam irradiation modified bonding layer is 5J/cm 2 、8J/cm 2 And 10J/cm 2 The energy density electron beam irradiation modified bonding layer can form nano particles, and the size of the nano particles is gradually reduced by 10J/cm along with the increase of energy 2 The number of nano particles on the surface of the energy density electron beam irradiation modified bonding layer is reduced;
then respectively testing the oxidation resistance of the original NiCrAlY bonding layer and the modified NiCrAlY bonding layer with different energy densities at 1150 ℃ by electron beam irradiation, and the result shows that the surface of the original NiCrAlY bonding layer can form continuous Al at the initial stage of oxidation 2 O 3 An oxide film, but a small amount of mixed oxide is doped in the oxide film, and the phenomenon of wrinkling of the oxide film is serious; the surface of the NiCrAlY bonding layer modified by electron beam irradiation with different energy densities can form a layer of continuous and compact Al 2 O 3 A protective film; in the later oxidation period, the original oxide film of the NiCrAlY bonding layer has serious peeling, serious internal oxidation and invalid coating; different fromThe oxide film on the surface of the energy density electron beam irradiation modified NiCrAlY bonding layer is still continuous and compact, wherein 3J/cm 2 The content of mixed oxide in the energy density electron beam irradiation modified bonding layer oxide film is higher, and a small amount of internal oxidation locally occurs, 5J/cm 2 8J/cm 2 The energy density electron beam irradiation modified bonding layer oxide film is the most compact, no internal oxidation and oxide film peeling phenomenon are seen, and the energy density electron beam irradiation modified bonding layer oxide film is 10J/cm 2 Small-area spalling occurs locally on the oxide film of the energy density electron beam irradiation modified bonding layer; in contrast, 5J/cm 2 8J/cm 2 The oxidation resistance of the energy density electron beam irradiation modified bonding layer is optimal, and the oxidation resistance of the bonding layer is improved by more than 1.5 times.
Example 3
The embodiment provides a preparation method of a thermal barrier coating bonding layer with high service life, which comprises the following steps:
(1) Grinding and polishing the surface of the superalloy substrate, ultrasonically cleaning the superalloy substrate with acetone and alcohol to remove greasy dirt, and then performing sand blasting treatment to obtain a pretreated superalloy substrate;
(2) Preparing an original NiCoCrAlYTA bonding layer on the surface of the pretreated high-temperature alloy substrate by adopting a low-pressure plasma spraying process, and selecting spraying parameters according to the preparation requirements of the bonding layer: the current is 1700A, the voltage is 55V, the power is 86kw, the powder feeding speed is 35g/min, and the spray distance is 500mm;
(3) Under the vacuum condition, the original NiCoCrAlYTA bonding layer is irradiated by adopting a pulse electron beam process, and irradiation parameters are selected according to irradiation modification requirements of the bonding layer: vacuum degree P is less than or equal to 5 multiplied by 10 -3 Pa, electron beam energy of 27KeV, pulse width of 1.5 μs, energy density of 8J/cm 2 The bombardment times are 30 times, and the irradiation modified NiCoCrAlYTA bonding layer is obtained, namely the thermal barrier coating bonding layer with long service life.
Observing the original NiCoCrAlYTA adhesive layer by adopting a three-dimensional confocal microscope, the surface roughness of the original NiCoCrAlYTA adhesive layer is up to 7.8 mu m, and the surface roughness of the irradiation modified NiCoCrAlYTA adhesive layer is greatly reduced and is only 1.28 mu m;
observing the original NiCoCrAlYTA adhesive layer and the irradiation modified NiCoCrAlYTA adhesive layer by adopting a scanning electron beam microscope, the surface of the original NiCoCrAlYTA adhesive layer is rough and uneven, more unmelted large particles exist, the surface of the irradiation modified NiCrAlY adhesive layer is thoroughly melted, the polishing effect is good, obvious nano crystal grains can be observed on the surface, and obvious vaporization is not seen; the original NiCoCrAlYTA bonding layer interface presents a layered structure, ta element aggregation phenomenon locally occurs, and the irradiation modified NiCrAlY bonding layer forms a melting layer with the thickness of about 10 mu m, and no element segregation phenomenon is found in the melting layer;
the detailed analysis of the original NiCoCrAlYTA bonding layer and the irradiation modified NiCoCrAlYTA bonding layer surface layer molten layer by using a transmission electron microscope shows that the internal elements of the original NiCoCrAlYTA bonding layer are unevenly distributed to locally form clustered substances, the irradiation modified NiCoCrAlYTA bonding layer forms evenly distributed Y enriched nano-dispersion particles, and the Ta element distribution is also quite even.
Then, respectively testing the high-temperature oxidation resistance of the original NiCoCrAlYTA bonding layer and the irradiation modified NiCoCrAlYTA bonding layer to obtain a morphology diagram of an oxide film in the 1150 ℃ high-temperature oxidation initial stage of the original NiCoCrAlYTA bonding layer in the embodiment 3 of the invention shown in FIG. 4 and a morphology diagram of an oxide film in the 1150 ℃ high-temperature oxidation initial stage of the irradiation modified NiCoCrAlYTA bonding layer in the embodiment 3 of the invention shown in FIG. 5; referring to FIGS. 4 and 5, it can be seen that the surface of the original NiCoCrAlYTA adhesive layer can form continuous Al at the initial stage of oxidation 2 O 3 Oxide film, but a large area of Ta segregation region appears in the oxide film (a large amount of Ta segregation is shown at the position of a virtual frame and the position of an arrow in FIG. 4), and the phenomenon of wrinkling of the oxide film is serious, and a continuous and compact Al layer can be formed on the surface of the irradiation modified NiCoCrAlYTA bonding layer 2 O 3 The protective film (the position TGO shown by the arrow in figure 5 is relatively flat, the position of the virtual frame shows only trace Ta segregation), and the oxidation resistance of the irradiation modified NiCoCrAlYTA bonding layer is improved by more than 2 times.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. The thermal barrier coating bonding layer with the high service life is characterized in that the bonding layer is a NiCoCrAlYTA bonding layer, and rare earth elements Y, ta in the bonding layer are uniformly distributed in the form of enriched nano particles; the enriched nanoparticles comprise Y-Al enriched nanoparticles;
the preparation method of the bonding layer comprises the following steps: after preparing a NiCoCrAlYTA bonding layer on the surface of a matrix by adopting a low-pressure plasma spraying process, carrying out irradiation treatment on the NiCoCrAlYTA bonding layer by adopting a pulse electron beam process, and eliminating the defect of uneven element distribution in the NiCoCrAlYTA bonding layer, so that rare earth elements in the bonding layer are uniformly distributed in the form of enriched nano particles, and the thermal barrier coating bonding layer with the long service life is obtained;
wherein, under vacuum condition, the NiCoCrAlYTA bonding layer is irradiated for multiple times by adopting a pulse electron beam process with short pulse width and low energy, the pulse width is 1-3 mu s, the energy of the electron beam is 20-30keV, and the energy density is 5-8J/cm 2 The irradiation times are 20-30 times;
the content of Y in the NiCoCrAlYTA bonding layer is at least 0.8wt%.
2. A method of preparing a high service life thermal barrier coating bond coat of claim 1, comprising: after preparing a NiCoCrAlYTA bonding layer on the surface of a substrate, carrying out irradiation treatment on the NiCoCrAlYTA bonding layer by adopting a pulse electron beam process, and eliminating the defect of uneven element distribution in the NiCoCrAlYTA bonding layer, so that rare earth elements in the bonding layer are uniformly distributed in the form of enriched nano particles, and the thermal barrier coating bonding layer with long service life is obtained;
wherein, a NiCoCrAlYTA bonding layer is prepared on the surface of the matrix by adopting a low-pressure plasma spraying process; under vacuum condition, the NiCoCrAlYTA bonding layer is subjected to multiple radiation by adopting a pulse electron beam process with short pulse width and low energyIrradiating, wherein the pulse width is 1-3 μs, the electron beam energy is 20-30keV, and the energy density is 5-8J/cm 2 The irradiation times are 20-30 times.
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