CN102660725B - Nano ceramic coating and preparation method thereof - Google Patents
Nano ceramic coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano ceramic coating and a preparation method thereof. The nano ceramic coating comprises the following components: 20-30wt% of CeO2, 6-9wt% of Y2O3, and the balance of ZrO2. Compared with the yttrium oxide stabilized zirconium oxide thermal barrier coating (ZrO2-Y2O3, YSZ) in the prior art, the nano ceramic coating (CSZ coating) prepared by adding nano CeO2 has the advantages that an interface exists between the added nano CeO2 and the ZrO2-Y2O3, more energy is needed for the growth of crystal grains, a high local stress exists between the un-molten nano CeO2 and the ZrO2-Y2O3 in the coating, and because dislocation is caused in a thermal expansion mismatch cooling period, a pinning function is achieved for the growth of the crystal grains to cause smaller crystal grains of the CSZ coating.
Description
Technical field
The invention belongs to ceramic coating technical field, particularly relate to a kind of nano ceramic coat and preparation method thereof.
Background technology
Thermal barrier coating is the low-down heat insulating coat of a kind of thermal conductivity, is coated on the parts surface under worst hot case condition, utilizes its thermal insulation protection effect can reduce the working temperature of coating lower substrate metal, improves the applied at elevated temperature performance and used life of parts.
The chemical composition of heat barrier coat material and microstructure are the important factors affecting coating performance.Meanwhile, the thermal conductivity of material is also a crucial evaluating, and the thermal conductivity of material is lower, and the effect of heat insulation of coating is better.The result of study of present stage shows, prepares in the material of thermal barrier coating in numerous kinds, and stupalith is (as Al
2o
3, ZrO
2deng) there is more excellent heat insulation and resistance toheat.But heat-proof quality and the Thermal fatigue properties of the thermal barrier coating adopting traditional ceramics material to prepare often can not meet the demands, research show micron and nanosized films due to the boundary scattering effect of conduction electron thus thermal conductivity reduce with the minimizing of film thickness, especially, when material is made up of nanoparticle, the large young pathbreaker of its thermal conductivity is by the serious restriction of boundary scattering.This illustrates that nanometer scale ceramics particle coating is in reduction thermal conductivity, improves heat-proof quality aspect and have larger potentiality compared with conventional ceramic coatings.
The main method preparing thermal barrier coating has electro beam physics vapour deposition method, laser cladding sends out method, Self-propagating high-temperature synthesis method, plasma spraying method etc., wherein plasma spraying is that ceramic powder is sent into very high temperature plasma flame, in melting or semi-melting state at a high speed spray to matrix, be set on matrix with speed of cooling faster, particle be the mutual mechanical snap of flat pie together, formed coating.It is little that it has facility investment, and technique is relatively simple, and coating and thickness are easy to control, to little by the restriction of spraying object size and dimension, and high work efficiency thus become the main method preparing nano ceramic coat.
Due to features such as nanoparticle specific surface area is large, surface energy is high, poor fluidities, directly nanometer powder is sent in plasma arc very difficult in thermal spray process, even if to enter in plasma flame flow nanoparticle also by gasification or fly upward, be difficult to deposit to matrix surface and form coating, therefore nanometer powder is not suitable for directly using as spray material, must reproduce and form macrobead nanometer aggregate powder of AI/Yt, then sintering forms the nanostructured feeds that can spray.It is comparatively ripe that current employing spray drying technology prepares aggregate powder of AI/Yt, and this technology can complete concentrated, dry, the granulation of liquid starting material within the several seconds, and the aggregate powder of AI/Yt made particle spherical in shape, good fluidity, water ratio is low.Nanometer aggregate powder of AI/Yt not only maintains the composition and structure of original Nano Ceramic Particles, and due to the increase of size and quality, and it is spherical in shape, significantly improve mobility, successfully solve the key technical problem adopting plasma spraying technology to prepare powder feeding difficulty in nano-structured coating process.
In Pulp preparation process, the problem of growing up of nanoparticle is the Focal point and difficult point that spray drying technology prepares nanostructured feeds, and especially how effectively realizing suppressing nanoparticle to be grown up while sintering densification is the key issue being badly in need of solving.But material system is as ZrO at present
2, Al
2o
3, TiO
2, Cr
2o
3easily grow up Deng in the preparation process of feeding, thus original nanostructure cannot be kept after spraying process.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of nano ceramic coat and preparation method thereof, and this coating solves the problem that nanoparticle is reunited and grown up.
The invention provides a kind of nano ceramic coat, comprise following composition:
CeO
220~30wt%；
Y
2O
36~9wt%；
Surplus is ZrO
2.
Preferably, described nano ceramic coat comprises: the CeO of 25wt%
2.
Preferably, described nano ceramic coat comprises: the Y of 8wt%
2o
3.
The invention provides a kind of preparation method of nano ceramic coat, comprise the following steps:
A) by CeO
2nanometer powder, Y
2o
3nanometer powder and ZrO
2nanometer powder utilizes Spray granulation method to prepare aggregate powder of AI/Yt;
B) described aggregate powder of AI/Yt is carried out plasma spraying, obtain nano ceramic coat.
Preferably, described steps A is specially:
A1) by CeO
2nanometer powder, Y
2o
3nanometer powder, ZrO
2nanometer powder and CH
2cH
2nH(PEI) mix in ethanol and stir, obtaining mixed serum;
A2) be that dry gas carries out centrifugal spray drying to described mixed serum with nitrogen, screening, obtain aggregate powder of AI/Yt after thermal treatment, heat treated temperature is 800 ~ 950 DEG C, and the time is 0.5 ~ 1.5h.
Preferably, in described steps A 2, heat treated temperature is 900 DEG C.
Preferably, in described steps A 2, the heat treated time is 1h.
The invention provides a kind of nano ceramic coat and preparation method thereof, this nano ceramic coat consists of: CeO
220 ~ 30wt%, Y
2o
36 ~ 9wt%, surplus is ZrO
2.With the Zirconium oxide heat barrier coating (ZrO of stabilized with yttrium oxide in prior art
2-Y
2o
3, YSZ) compare, add nano Ce O in the present invention
2be prepared into ternary nano ceramic coating (CSZ coating), the nano Ce O first added
2and ZrO
2-Y
2o
3between Presence of an interface, growing up of crystal grain needs energy more, secondly not molten in coating nano Ce O
2and ZrO
2-Y
2o
3between there is high local stress, due to thermal expansion mismatch cooling period produce dislocation, have " pinning " to act on to growing up of crystal grain, cause CSZ coated grains less.
Experimental result shows, the average grain size of ceramic coating prepared by the present invention is 58.6nm, and the shell of melting is the very strong columnar crystal structure of directivity, and be micrometer structure, inside remains original ternary Y
2o
3-ZrO
2-CeO
2nano Ceramic Particles, mean sizes is 45nm; The porosity average out to 7.3% of CSZ coating; The most high bond strength of coating is 60MPa, and average heat-insulating capability is 110 DEG C, and thermal shock resistance is 12 times.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 raw material CeO
2the transmission electron microscope photo of nanometer powder;
Fig. 2 is the embodiment of the present invention 1 raw material ZrO
2-8wt%Y
2o
3the transmission electron microscope photo of nanometer powder;
Fig. 3 is the embodiment of the present invention 1 raw material CeO
2the X ray diffracting spectrum of nanometer powder;
Fig. 4 is the embodiment of the present invention 1 raw material ZrO
2-8wt%Y
2o
3the X ray diffracting spectrum of nanometer powder;
Fig. 5 is the X ray diffracting spectrum of aggregate powder of AI/Yt prepared by the embodiment of the present invention 1;
Fig. 6 is the X ray diffracting spectrum of reunion powder after the spraying of the embodiment of the present invention 1 preparation;
Fig. 7 is the stereoscan photograph of aggregate powder of AI/Yt prepared by the embodiment of the present invention 1;
Fig. 8 is the stereoscan photograph of aggregate powder of AI/Yt prepared by the embodiment of the present invention 1;
Fig. 9 is the stereoscan photograph of reunion powder after the spraying of the embodiment of the present invention 1 preparation;
Figure 10 is the field emission scanning electron microscope photo of reunion powder fracture after the spraying of the embodiment of the present invention 1 preparation;
Figure 11 is the field emission scanning electron microscope photo of reunion powder fracture after the spraying of the embodiment of the present invention 1 preparation;
Figure 12 is the field emission scanning electron microscope photo of reunion powder melting shell after the spraying of the embodiment of the present invention 1 preparation;
Figure 13 is the field emission scanning electron microscope photo of reunion powder melting outer casing inner wall after the spraying of the embodiment of the present invention 1 preparation;
Figure 14 is the backscattered electron imagine photo in CSZ thermal barrier coating weave construction cross section prepared by the embodiment of the present invention 2;
Figure 15 is the backscattered electron imagine photo of CSZ ceramic layer weave construction prepared by the embodiment of the present invention 2;
Figure 16 is the stereoscan photograph of CSZ thermal barrier coating prepared by the embodiment of the present invention 2;
Figure 17 is the stereoscan photograph in CSZ thermal barrier coating A district prepared by the embodiment of the present invention 2;
Figure 18 is the field emission scanning electron microscope photo in CSZ thermal barrier coating B district prepared by the embodiment of the present invention 2;
Figure 19 is the field emission scanning electron microscope photo of CSZ thermal barrier coating melting area prepared by the embodiment of the present invention 2;
Figure 20 is CSZ coating X ray diffracting spectrum prepared by the embodiment of the present invention 2;
Figure 21 is the YSZ coating X ray diffracting spectrum of comparative example 1 of the present invention preparation;
Figure 22 is CSZ thermal barrier coating bonding strength curve prepared by the embodiment of the present invention 2 ~ 4;
Figure 23 is CSZ thermal barrier coating heat-proof quality curve prepared by the embodiment of the present invention 2 ~ 4;
Figure 24 is CSZ thermal barrier coating thermal shock performance column diagram prepared by the embodiment of the present invention 2 ~ 4.
Embodiment
The invention provides a kind of nano ceramic coat, it consists of: CeO
220 ~ 30wt%, Y
2o
36 ~ 9wt%, surplus is ZrO
2.
Wherein CeO
2content is preferably 25wt%, Y
2o
3content is preferably 8wt%.
Stupalith ZrO
2there is excellent heat insulation and resistance toheat, but pure ZrO
2there is different phase structures at different temperature, high temperature cubic phase ZrO
2can tetragonal crystal be changed in process of cooling, when temperature reduces further, monoclinic crystal can be become mutually again, when tetragonal phase converting is monoclinic phase, volume can increase 4% ~ 6%, thus can cause high pressure stress, easily cause the formation of crackle and the damage of material, therefore the close Y of ionic radius need be added
2o
3as stablizer.
Its preparation method comprises the following steps:
A) by CeO
2nanometer powder, Y
2o
3nanometer powder and ZrO
2nanometer powder utilizes Spray granulation method to prepare aggregate powder of AI/Yt;
B) described aggregate powder of AI/Yt is carried out plasma spraying, obtain nano ceramic coat.
Nano Ce O is added in the present invention
2be prepared into CSZ coating, the nano Ce O first added
2and ZrO
2-Y
2o
3between Presence of an interface, growing up of crystal grain needs energy more, secondly not molten in coating nano Ce O
2and ZrO
2-Y
2o
3between there is high local stress, due to thermal expansion mismatch cooling period produce dislocation, have " pinning " to act on to growing up of crystal grain, cause CSZ coated grains less.
In order to clearly demonstrate the present invention, respectively the experimentation of steps A is described in detail below.
According to the present invention, wherein said steps A is specially:
A1) by CeO
2nanometer powder, Y
2o
3nanometer powder, ZrO
2nanometer powder and CH
2cH
2nH(PEI) mix in ethanol and stir, obtaining mixed serum;
A2) be that dry gas carries out centrifugal spray drying to described mixed serum with nitrogen, screening, obtain aggregate powder of AI/Yt after thermal treatment, heat treated temperature is 800 ~ 950 DEG C, and the time is 0.5 ~ 1.5h.
Wherein in steps A 2, heat treated temperature is preferably 900 DEG C, and the time is preferably 1h.
The average grain size of nano ceramic coat prepared by the present invention is 58.6nm, and the shell of melting is the very strong columnar crystal structure of directivity, and be micrometer structure, inside remains original ternary Y
2o
3-ZrO
2-CeO
2nano Ceramic Particles, mean sizes is 45nm; The porosity average out to 7.3% of CSZ coating; The most high bond strength of coating is 60MPa, and average heat-insulating capability is 110 DEG C, and thermal shock resistance is 12 times.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of nano ceramic coat provided by the invention and preparation method thereof is described in detail.
In following examples, body material nickel base superalloy plate is provided with compensation by Fushun Special Steel Shares Co., Ltd, and its chemical composition is as shown in table 1; Metal bonding coating NiCrAlY powdered alloy is provided by Shenyang Inst. of Metals, Chinese Academy of Sciences, and size range is 45 μm ~ 75 μm, and its chemical composition is as shown in table 2; ZrO
2nanometer powder and Y
2o
3nanometer powder is provided by Wuhan Inst. of Material Protection; CeO
2nanometer powder is provided by Guangzhou Research Institute of Nonferrous Metals; The GP-80 type plasma spray system that spraying equipment is produced for Beijing 625.
The chemical composition (%) of table 1 nickel base superalloy (GH30)
The chemical composition (%) of table 2NiCrAlY powder
Embodiment 1
1.1ZrO
2-8wt%Y
2o
3-25wt%CeO
2the preparation of aggregate powder of AI/Yt
1.1.1 by 25wt%CeO
2nanometer powder, 8wt%Y
2o
3nanometer powder, 67wt%CeO
2and CH
2cH
2nH(PEI) mix in ethanol and stir, obtaining mixed serum, wherein CH
2cH
2nH(PEI) as tackiness agent.
1.1.2 be that dry gas carries out centrifugal spray drying to the mixed serum obtained in 1.1.1 with nitrogen, screening, obtains ZrO after thermal treatment 1h under 900 DEG C of conditions
2-8wt%Y
2o
3-25wt%CeO
2aggregate powder of AI/Yt, size range is 40 μm-85 μm.
1.2 plasma spraying
Spray gun is controlled by robot (YASKAWA Motorman UP-6), large granular spherical nanoclusters aggressiveness is sprayed into Quench in 25 DEG C of water by plasma gun with the distance that 80mm, 100mm, 120mm, 150mm are different, and collect this powder particle, Plasma Spray Parameters is as shown in table 3.
Utilize transmission electron microscope to CeO
2nanometer powder and ZrO
2-8wt%Y
2o
3nanometer powder is analyzed, and obtains the transmission electron microscope photo of original nanometer powder, respectively as depicted in figs. 1 and 2.By analyzing, original nanometer powder size-grade distribution is 20 ~ 50nm.
Utilize X-ray (XRD) diffractometer to original CeO
2nanometer powder and ZrO
2-8wt%Y
2o
3after nanometer powder, aggregate powder of AI/Yt and plasma spraying, the phase structure of powder is analyzed, and obtains the XRD analysis figure of powder after original nanometer powder, aggregate powder of AI/Yt and plasma spraying, respectively as Fig. 3,4, shown in 5 and 6.From diffraction patterns, original CeO
2nanometer powder has cubic crystal structure (c-CeO
2), original ZrO
2-8wt%Y
2o
3nanometer powder is primarily of tetragonal (t-ZrO
2) and oblique crystal (m-ZrO
2); Two kinds of crystal formation compositions; Aggregate powder of AI/Yt phase composite is still mainly c-CeO
2, t-ZrO
2and m-ZrO
2, have (CeZr) O of a small amount of cubic crystal in addition
2formed; After spraying, powder is primarily of t-ZrO
2, c-CeO
2with sosoloid Zr
0.88ce
0.12o
2composition.M-ZrO in original nano ceramic powder and aggregate powder of AI/Yt
2substantially, disappear, this mainly contains the reason of two aspects: first, in Plasma Spraying Process Using, and original m-ZrO in nano ceramic powder
2tetragonal t-ZrO is changed in high-temperature heating process
2, but cooling inhibits the transformation of t → m fast, still keeps t phase structure when being chilled to room temperature; Secondly, CeO
2acid strong, and in mixed powder, content is higher, thus strong to the stabilization of t phase, and Y
2o
3t phase during jointly stabilizing high temperature.
XRD live width method meter is utilized to calculate the aggregate powder of AI/Yt nanoparticle mean grain size of aggregate powder of AI/Yt after Overheating Treatment, can find out that coacervate nanoparticle mean particle size is that 42nm conforms to the statistics of original nanometer powder size-grade distribution according to calculation result, show that the Nano Ceramic Particles forming aggregate powder of AI/Yt after Overheating Treatment is consistent with original nanoparticle average dimension, after Overheating Treatment, do not make Nano Ceramic Particles grow up.
Utilize scanning electron microscope to analyze powder after aggregate powder of AI/Yt and spraying, obtain aggregate powder of AI/Yt and powder scanning electron microscopic picture after spraying, as shown in Figure 7, Figure 8 and Figure 9.By com-parison and analysis electromicroscopic photograph, can find out that aggregate powder of AI/Yt leaves hole due to tackiness agent volatilization after thermal treatment, spherical powder surface becomes coarse, loose structure.
Utilize the shell tissue of field emission scanning electron microscope (FESEM) to the not molten part of powder after spraying and melting to analyze, obtain its FESEM electromicroscopic photograph, as shown in Figure 10 ~ 13.By com-parison and analysis FESEM electromicroscopic photograph, the pattern of molten part and reunite front powder morphology, consistent size can be found out, therefore can determine that melting the enclosure interior formed remains original Nano Ceramic Particles, after plasma spraying, just top layer has melted about 2 ~ 4 μm, the shell of melting is the very strong columnar crystal structure of directivity, and heat dissipation direction when its direction of growth and cooling is consistent.Thus the thermal barrier coating obtaining having nanostructure with nanometer aggregate powder of AI/Yt after plasma spraying can be determined.
Embodiment 2 ~ 4
2.1 prepare aggregate powder of AI/Yt in the mode that embodiment 1 is same.
After 2.2 matrix alloy nickel base superalloy plates (GH30) do sandblasting roughening treatment, with plasma spraying method spraying tack coat NiCrAlY powdered alloy.Tack coat is used for relaxing the difference of thermal expansivity between ceramic coating and matrix metal, improves resistance to high temperature corrosion and the oxidation susceptibility of matrix metal.Plasma Spray Parameters is as shown in table 3.
2.3 plasma spraying
Spray gun is controlled by robot (YASKAWA Motorman UP-6), large granular spherical nanoclusters aggressiveness is sprayed on 2.2 by plasma gun to be coated with on the matrix alloy of tack coat, Plasma Spray Parameters is as shown in table 3, obtains 100 μm, 300 μm, 500 μm thick nano ceramics thermal barrier coatings.
Table 3 Plasma Spray Parameters
Comparative example 1
With ZrO
2-8wt%Y
2o
3nanometer powder is raw material, and the method same with embodiment 2 ~ 4 and parameter prepare traditional YSZ coating.
Utilize backscattered electron imagine technology to analyze the CSZ thermal barrier coating cross section that embodiment 2 obtains, obtain the backscattered electron image of whole coating structure and ceramic structure, as shown in Figure 14 and Figure 15.Can find out that complete thermal barrier coating comprises ceramic layer and tack coat by picture.Due to matrix alloy before spraying through sandblasting roughening treatment, microcosmic is rough, NiCrAlY powdered alloy through plasma arc by heat fused, high-speed impact is to matrix surface, liquid metal is sprawled along rough high-temperature alloy surface, and define between matrix good " grasp effect ", be conducive to improving the bonding strength between coating and matrix.The laminar structured of tack coat is because the intermittence of plasma spraying is formed; Tack coat does not have tiny crack to be because NiCrAlY is metal alloy, in Plasma Spraying Process Using, metal powder granulates melting ratio is comparatively complete, and the powder particle of fusing produces distortion after encountering matrix, and tiling property is good, show as tack coat even, fine and close, hole is less.There are some irregular closed holes in ceramic layer.Reunite nano particle through plasma arc part larger particles be that top layer is melted, inside is still multi-pore structure during reunion, the shell melted when clashing into matrix is not enough to pore filling, unfused nano particle and this hole are covered formation hole, deposited particles afterwards constantly covers, become closed hole, make whole coating without penetrability perforate.The existence of hole can make ceramic density reduction, thermal conductivity reduces, thermal shock performance improves.But hole is also area of stress concentration, directly may become crackle, ceramic layer intensity is reduced.If ceramic layer hole is too much, be easily connected to form penetrability cavity, ambient atmos is easy to the interface reaching surface layer/tack coat under the high temperature conditions, causes tie layer surface oxide growth to be accelerated, thermal stresses increase, and coating easily ftractures stripping.The porous nickel of nanometer CSZ coating, approximate circle ball-type, favourable to reduction thermal conductivity, be conducive to avoiding stress concentration, improving thermal shock resistance.As seen from the figure, tiny crack tiny in a large number and canescence ribbon tissue is distributed with in ceramic layer.
Mechanically nanometer CSZ coating is stripped down from matrix surface, then fracture sample is made, scanning electron microscope and field emission scanning electron microscope is utilized to analyze it, obtain the photo of scanning electron microscope and field emission scanning electron microscope, as shown in Figure 16 ~ 19, wherein coating is divided into the A district of melting crystal and unfused B district as can be seen from Figure 16, and B district is consistent with original nanometer powder form as can be seen from Figure 18, for the particle of 20nm ~ 50nm, still keep nanostructure.A district is made up of the column crystal that directivity is very strong as can be seen from Figure 19.The formation of this tissue is because nanometer aggregate powder of AI/Yt is in spraying process, short by the time compole of high-temperature plasma flame stream, be that surperficial one deck is melted for larger nanoclusters interpolymer particles, the top layer of fusing is wrapped up in and is taken not molten nanometer powder and be sprayed onto workpiece surface, and shell crystallisation by cooling and the unfused nanoparticle of melting after clashing into mix.
The YSZ coating that the nanometer CSZ coating utilizing X-ray diffraction technology to obtain embodiment 2 and comparative example 1 obtain, obtains both X-ray diffraction result figure, as shown in Figure 20 and Figure 21.Can find out by analyzing, in CSZ nano coating, the composition of phase is different with the composition in embodiment 1, and in coating, phase composite is t-ZrO
2, c-CeO
2, t-Y
0.1ceO
0.9o
1.95and t-Zr
0.82ce
0.18o
2, this is because agglomerating particles to spray into the strain produced in water less, and through strain that plasma arc high temperature deposition produces when the particle of high-temperature alloy surface contacts with water much larger than agglomerating particles due to strain that high-speed impact matrix produces; In addition, the unrelieved stress accumulative in deposition process repeatedly of coating is also comparatively large, also has impact to phase transformation.Although therefore with same spraying coating process, after spraying, powder is different with the phase composite of coating.The grain-size recorded through X-ray diffraction can find out that CSZ nano coating grain-size is grown up less, this is because: first, the nano Ce O of interpolation
2and ZrO
2-Y
2o
3between Presence of an interface, grain growth needs higher energy; Secondly, coating nano Ce O
2and ZrO
2-Y
2o
3thermal expansion mismatch produces high local stress, makes cooling period produce dislocation, has " pinning " to act on to growing up of crystal grain; Again, rate of cooling high in spraying process result in high nucleation rate, inhibits growing up of crystal grain simultaneously.
Utilize XRD live width method meter to calculate the mean grain size of CSZ coating, the average grain size obtaining ceramic coating is 58.6nm, and the shell of melting is the very strong columnar crystal structure of directivity, and be micrometer structure, inside remains original ternary Y
2o
3-ZrO
2-CeO
2nano Ceramic Particles, mean sizes is 45nm.
Nikon metallurgical analysis system is utilized to carry out analysis of porosity to nanometer CSZ coating and traditional YSZ coating.Porosity is mainly used to the compactness evaluating coating, is one of important indicator weighing coating quality.Through the image of binary conversion treatment through Nikon metallurgical analysis software analysis, obtain the porosity average out to 7.3% of CSZ coating, and traditional YSZ porosity average out to 11.4%.
The micron-sized ceramic heat-barrier coating of 100 μm, 300 μm that obtain embodiment 2 ~ 4 according to rower HB5476-91,500 μm thick nano ceramics thermal barrier coatings and same raw material carries out bonding strength test, and the experimental result obtained as shown in figure 22.Can find out by analyzing, the bonding strength of two kinds of ceramic heat-barrier coatings is all relevant with the thickness of ceramic coating, reduces with the increase of thickness.The bonding strength of 100 μm, 300 μm, 500 μm thick nano ceramics thermal barrier coatings is respectively: 65MPa, 60MPa and 47MPa, and the bonding strength of the micron-sized ceramic heat-barrier coating of respective thickness is respectively: 48MPa, 42MPa and 32MPa, nano level bonding strength on average improves 30%.This main because: under stress, nanocrystal can occur to slide or rotate, and has certain stress relief effect, the stress of nano ceramic coat is obviously reduced; Nanometer aggregate powder of AI/Yt improves the binding ability with basal plane through plasma spraying.
The micron-sized ceramic heat-barrier coating of 100 μm, 300 μm that obtain embodiment 2 ~ 4 respectively, 500 μm thick nano ceramics thermal barrier coatings and same raw material carries out heat-proof quality test, and when obtaining Coated Surface Temperature about 900 DEG C, the experimental result of thermal barrier coating heat-proof quality as shown in figure 23.From experimental result, when nano coating thickness is respectively 100 μm, 300 μm, 500 μm, the temperature head at ceramic coating surface and the matrix back side is respectively 87 DEG C, 110 DEG C, 118 DEG C, the temperature difference of micro-ceramic thermal barrier coating is then respectively 60 DEG C, 67 DEG C, 92 DEG C, the heat-proof quality of nano ceramics thermal barrier coating significantly improves, and may be because the boundary scattering of nanocrystalline bound pair conduction electron causes its thermal conductivity to reduce.
The micron-sized ceramic heat-barrier coating of 100 μm, 300 μm that utilize rower HB7269-96 to obtain embodiment 2 ~ 4,500 μm thick nano ceramics thermal barrier coatings and same raw material carries out thermal shock performance test, obtain it 1100 DEG C of thermal shock performance test-results, as shown in figure 24.As can be seen from experimental result, during CSZ coat-thickness 100 μm, all there is not holiday through 20 thermal shocks circulation in nanometer and micro-ceramic thermal barrier coating; During coat-thickness 300 μm, the thermal shock cycle index of nano ceramics thermal barrier coating is 12, and the thermal shock cycle index of micro-ceramic thermal barrier coating is 2; Coat-thickness is 500 μm, and the thermal shock cycle index of nanometer, micro-ceramic thermal barrier coating is respectively 6 and 1, and the thermal shock performance of nano ceramics thermal barrier coating comparatively micron order thermal barrier coating significantly improves.This mainly because: there is the stupalith of nanostructure under thermal cycling stresses effect, nanocrystal can occur slide or rotate, there is certain stress relief ability, the fragility of nano ceramic coat obviously reduced; Nanoparticle makes ceramic coating toughness improve, and reduces the propagation rate of crackle; The existence of nanocrystal in coating, improves the bonding strength of coating interface.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a nano ceramic coat, is characterized in that, comprises following composition:
CeO
220~30wt%；
Y
2O
36~9wt%；
Surplus is ZrO
2.
2. nano ceramic coat according to claim 1, is characterized in that, comprising:
The CeO of 25wt%
2.
3. nano ceramic coat according to claim 1, is characterized in that, comprising:
The Y of 8wt%
2o
3.
4. a preparation method for the nano ceramic coat described in any one of claim 1 ~ 3, is characterized in that, comprises the following steps:
A) by CeO
2nanometer powder, Y
2o
3nanometer powder and ZrO
2nanometer powder utilizes Spray granulation method to prepare aggregate powder of AI/Yt;
B) described aggregate powder of AI/Yt is carried out plasma spraying, obtain nano ceramic coat.
5. preparation method according to claim 4, is characterized in that, described steps A is specially:
A1) by CeO
2nanometer powder, Y
2o
3nanometer powder, ZrO
2nanometer powder and CH
2cH
2nH(PEI) mix in ethanol and stir, obtaining mixed serum;
A2) be that dry gas carries out centrifugal spray drying to described mixed serum with nitrogen, screening, obtain aggregate powder of AI/Yt after thermal treatment, heat treated temperature is 800 ~ 950 DEG C, and the time is 0.5 ~ 1.5h.
6. preparation method according to claim 5, is characterized in that, in described steps A 2, heat treated temperature is 900 DEG C.
7. preparation method according to claim 5, is characterized in that, in described steps A 2, the heat treated time is 1h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210171490.2A CN102660725B (en) | 2012-05-29 | 2012-05-29 | Nano ceramic coating and preparation method thereof |
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|---|---|---|---|
| CN201210171490.2A CN102660725B (en) | 2012-05-29 | 2012-05-29 | Nano ceramic coating and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102660725A CN102660725A (en) | 2012-09-12 |
| CN102660725B true CN102660725B (en) | 2015-02-04 |
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| CN104496470B (en) * | 2014-12-16 | 2017-01-18 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method of high-elasticity nano zirconia-base ceramic |
| CN108950462A (en) * | 2018-08-17 | 2018-12-07 | 滁州欧瑞斯机车部件有限公司 | A kind of preparation method in friction material steel back surface spraying composite ceramics insulating layer |
| CN109207917B (en) * | 2018-10-19 | 2020-08-04 | 南京航空航天大学 | NiCrAlSi/CeO2Doped YSZ thermal barrier coating and preparation method thereof |
| CN110129709B (en) * | 2019-06-11 | 2021-09-10 | 华东理工大学 | Preparation method of ceramic layer, ceramic layer obtained by preparation method and thermal barrier coating of ceramic layer |
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