CN103434209B - A kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof - Google Patents
A kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof Download PDFInfo
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- CN103434209B CN103434209B CN201310396194.7A CN201310396194A CN103434209B CN 103434209 B CN103434209 B CN 103434209B CN 201310396194 A CN201310396194 A CN 201310396194A CN 103434209 B CN103434209 B CN 103434209B
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Abstract
The invention belongs to high temperature coating guard technology field, particularly a kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof.The present invention adopts Pr
2zr
2o
7the ceramic top layer that system is formed.Due to Pr
2zr
2o
7the new ceramics top layer that system is formed has the structure similar with the pyrochlore mineral structure that nature exists, and this kind of structure has complex structure, low thermal conductivity, high-melting-point, high thermal coefficient of expansion and good phase stability.Therefore Pr is adopted
2zr
2o
7have low thermal conductivity as ceramic top layer, high thermal coefficient of expansion and the advantage such as stable mutually, can apply thermal barrier coating system in high temperature environments.The thermal barrier coating of different-thickness can be obtained according to the difference of preparation technology, thus obtain different effect of heat insulation, reach the object required for commercial Application.This coating has good high temperature resistant, low heat conduction and the advantage of high thermal coefficient of expansion, also has the performance that certain high temperature resistant CMAS corrodes simultaneously.
Description
Technical field
The invention belongs to high temperature coating guard technology field, particularly a kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof.
Background technology
The development of modern technologies, more and more higher to the expectation of aeronautical and space technology, thus more and more higher requirement is proposed to aero-engine performance, namely also require increasing to the thrust-weight ratio of engine, require also more and more higher to the revolution of aero-engine, therefore the out temperature improving turbine just seems particularly important, but work under the condition of higher temperature, the temperature that the nickel-base high-temperature alloy material having exceeded manufacture turbo blade and guide vane can bear, compared with the high temperature alloy new with exploitation, Thermal Barrier Coating Technologies (thermalbarriercoatings, TBCs) research cost is much lower, technique practicable, therefore, application Thermal Barrier Coating Technologies is one of direction of turbine development.
Generally use in aero-engine at present and there is the good double-decker thermal barrier coating of good stability, effect of heat insulation, namely adopt and between ceramic layer and metallic matrix, to introduce one deck improve matrix and ceramic layer physical compatibility and the tack coat (NiCoCrAlY) with resistance to high temperature oxidation and corrosiveness, with by (7 ~ 9wt%) stabilized with yttrium oxide, zirconia that heat-insulating capability is strong (YttriaStabilizedZirconia is called for short YSZ) pottery is as heat insulation top layer.YSZ during Long-Time Service, can undergo phase transition more than 1200 DEG C, sinters and causes tack coat to be oxidized the aggravation imagination.But aero-engine out temperature of future generation will significantly improve, estimate that the thrust-weight ratio when engine reaches 20, fuel gas inlet temperature will more than 2000 DEG C.Use at such high temperatures, the material system that inevitable requirement can match with it, because rear-earth-doped YSZ has lower thermal conductivity and stable high-temperature behavior, therefore, design rear-earth-doped resistant to elevated temperatures lower thermal conductivity thermal barrier coating and there is important scientific meaning and social value.
Summary of the invention
Not enough for prior art, the invention provides a kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof.
Novel lower thermal conductivity and a high temperature heat-resistant barrier coating, described thermal barrier coating is double-decker, and wherein NiCoCrAlY is as adhesive linkage, Pr
2zr
2o
7as ceramic top layer, the two is connected and forms; In described NiCoCrAlY adhesive linkage, the mass fraction of the mass fraction of Co to be the mass fraction of 22% ~ 24%, Cr be 20% ~ 22%, Al is the mass fraction of 8% ~ 10%, Y is 0.5% ~ 1.5%, and all the other are Ni.
Described Pr
2zr
2o
7ceramic top layer has the structure same with pyrochlore mineral facies.
Described Pr
2zr
2o
7the thermal conductivity of ceramic top layer is 1.6 ~ 1Wm
-1k
-1, its fusing point is 2350 DEG C, and its thermal coefficient of expansion is 11 ~ 5K
-1.
A preparation method for novel lower thermal conductivity and high temperature heat-resistant barrier coating, its concrete steps are as follows:
(1) preparation of NiCoCrAlY tack coat, adopts one of following two schemes:
A. the technique adopting electro beam physics vapour deposition technology to prepare NiCoCrAlY tack coat is: the raw material configured is carried out high melt at 1500 ~ 1600 DEG C of temperature, NiCoCrAlY charge bar is cast into after melting, in described raw material, the mass fraction of Co is 22% ~ 24%, the mass fraction of Cr is 20% ~ 22%, the mass fraction of Al is 8% ~ 10%, the mass fraction of Y is 0.5% ~ 1.5%, and all the other are Ni; Gained NiCoCrAlY charge bar is put into electro beam physics vapour deposition vacuum chamber, is 1 × 10 by the vacuum degree control of vacuum chamber
-2~ 10 × 10
-2pa, deposits with the speed of 0.1 ~ 2 μm/min; Deposition time substrate temperature controls to be 800 ~ 900 DEG C, and it is 60 ~ 90 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into vacuum drying oven and heat-treats; Described Technology for Heating Processing is: vacuum degree control is 1 × 10
-2~ 10 × 10
-2pa, heating rate is 3 DEG C/min, at 1050 DEG C, be incubated 4 hours, after stove cooling, can obtain NiCoCrAlY tack coat;
B. the technological parameter adopting plasma spraying technology to prepare NiCoCrAlY tack coat is: voltage is 50 ~ 60V, electric current is 500 ~ 600A, argon flow amount is 50 ~ 60L/min, powder feeding rate is 20 ~ 40g/min, in the raw material used, the mass fraction of the mass fraction of Co to be the mass fraction of 22% ~ 24%, Cr be 20% ~ 22%, Al is 8% ~ 10%, the mass fraction of Y is 0.5% ~ 1.5%, and all the other are Ni;
(2) blasting treatment of NiCoCrAlY tack coat:
Carry out blasting treatment in the NiCoCrAlY tie layer surface prepared, its blasting craft is: angle is 90 degree, and distance is 200mm, and sand grains is 60 ~ 180 object emergies, and the time is 3 minutes;
(3) with the NiCoCrAlY tack coat after blasting treatment for substrate, prepare Pr thereon
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating, adopt one of following two schemes:
A. by Pr
2o
5powder is doped in zirconia, wherein Pr
2o
5the mass fraction of powder is 10% ~ 30%, after stirring, and is under the condition of 0.6MPa at pressure, 10 hours are sintered at 1500 DEG C of temperature, carry out high temperature insostatic pressing (HIP), obtain the charge bar needed for electro beam physics vapour deposition, then adopt electro beam physics vapour deposition to prepare Pr
2zr
2o
7ceramic top layer;
Described electro beam physics vapour deposition technique is: by the Pr of synthesis
2zr
2o
7being charge bar, putting into electro beam physics vapour deposition vacuum chamber, is 1 × 10 by the vacuum degree control of vacuum chamber
-2~ 10 × 10
-2pa, deposits with the speed of 0.1 ~ 2 μm/min; During deposition, NiCoCrAlY tack coat base reservoir temperature controls is 800 ~ 900 DEG C, and it is 80 ~ 100 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into stove and heat-treats; Described Technology for Heating Processing is: heating rate is 3 DEG C/min, is incubated 2 hours at 1050 DEG C, after stove cooling, can prepare Pr
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating;
B. by Pr
2o
5be doped in Zirconium powder, wherein Pr
2o
5mass fraction be 10% ~ 30%, the granularity of described Zirconium powder is 1 ~ 10 μm, after stirring, and obtains the ceramic top layer powder needed for plasma spraying, adopt plasma spraying prepare Pr
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating;
The technological parameter of described plasma spraying is: voltage is 50 ~ 60V, electric current is 500 ~ 600A, argon flow amount is 50 ~ 60L/min, hydrogen flowing quantity is 15 ~ 25L/min, turntable rotating speed is 5 ~ 15 turns/min, spray gun rotating speed is 35 ~ 45 turns/min, and cavity pressure is 70 torrs, and powder feeding rate is 20 ~ 40g/min.
In step (1), described NiCoCrAlY charge bar is of a size of Φ 68mm × 200mm.
Beneficial effect of the present invention is:
Electro beam physics vapour deposition technology or plasma spraying technology is utilized to prepare Pr
2zr
2o
7the ceramic top layer that system is formed, due to Pr
2zr
2o
7the ceramic top layer that system is formed has the structure similar with pyrochlore mineral structure, and this kind of structure has complex structure, low thermal conductivity, high-melting-point, high thermal coefficient of expansion and good phase stability.The principle that this kind of structure has lower thermal conductivity is the thermal resistance coefficient of insulator is vibrated by the point of phon scattering to determine, reduce the vibration of one of mode of thermal conductivity interference dot matrix, change into crystallization atoms different in relative low-symmetry or structure cell when crystal structure to combine, the quantity of interfering scattering center increases in addition, and thermal conductivity will decline.So crystal structure becomes more complicated, thermal conductivity will be lower.Thus can be used in preparing the Novel hot barrier coating at high temperature applied.Utilize different technique adjustment thermal barrier coatings, to reach industrial requirement simultaneously.This thermal barrier coating has good high temperature resistant, low heat conduction and the advantage of high thermal coefficient of expansion, also has the performance that certain high temperature resistant CMAS corrodes simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural representation of thermal barrier coating of the present invention.
Detailed description of the invention
The invention provides a kind of novel lower thermal conductivity and high temperature heat-resistant barrier coating and preparation method thereof, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
The raw material configured is carried out high melt at 1500 ~ 1600 DEG C of temperature, is cast into NiCoCrAlY charge bar after melting, in described raw material, the mass fraction of Co is 22%, the mass fraction of Cr is 20%, the mass fraction of Al is the mass fraction of 8%, Y is 0.5%, and all the other are Ni; Being cast into the charge bar being of a size of Φ 68mm × 200mm after melting, gained NiCoCrAlY charge bar is put into electro beam physics vapour deposition vacuum chamber, is 1 × 10 by the vacuum degree control of vacuum chamber
-2pa, deposits with the speed of 0.1 μm/min; Deposition time substrate temperature controls to be 800 ~ 900 DEG C, and it is 60 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into vacuum drying oven and heat-treats; Described Technology for Heating Processing is: vacuum degree control is 1 × 10
-2pa, heating rate is 3 DEG C/min, at 1050 DEG C, be incubated 4 hours, after stove cooling, can obtain NiCoCrAlY tack coat;
Carry out blasting treatment in the NiCoCrAlY tie layer surface prepared, its blasting craft is: angle is 90 degree, and distance is 200mm, and sand grains is 60 ~ 180 object emergies, and the time is 3 minutes, thus obtains desirable NiCoCrAlY adhesive linkage surface;
With the NiCoCrAlY tack coat after blasting treatment for substrate, adopt electro beam physics vapour deposition technology to prepare ceramic top layer thereon, its concrete technology is: by Pr
2o
5powder is doped in zirconia, wherein Pr
2o
5the mass fraction of powder is 10%, after stirring, and is under the condition of 0.6MPa at pressure, sinters 10 hours, carry out high temperature insostatic pressing (HIP) at 1500 DEG C of temperature, forms the charge bar needed for electro beam physics vapour deposition, by the Pr of synthesis
2zr
2o
7be ceramic rod, put into electro beam physics vapour deposition vacuum chamber, by the vacuum degree control of vacuum chamber 2 × 10
-2pa, deposit with the speed of 0.8 μm/min, in order to obtain better bond strength and coating structure pattern, during deposition, NiCoCrAlY tack coat base reservoir temperature controls at about 850 DEG C, and coating layer thickness controls at about 90 μm, after the made sample got ready is cooled down, put into stove to heat-treat, its treatment process is: heating rate is 3 DEG C/min, is incubated 2 hours at 1050 DEG C, after stove cooling, namely can be made into required novel high temperature resistance thermal barrier coating.
Embodiment 2
The raw material configured is carried out high melt at 1500 ~ 1600 DEG C of temperature, is cast into NiCoCrAlY charge bar after melting, in described raw material, the mass fraction of Co is 23%, the mass fraction of Cr is 21%, the mass fraction of Al is the mass fraction of 9%, Y is 1%, and all the other are Ni; Being cast into the charge bar being of a size of Φ 68mm × 200mm after melting, gained NiCoCrAlY charge bar is put into electro beam physics vapour deposition vacuum chamber, is 5 × 10 by the vacuum degree control of vacuum chamber
-2pa, deposits with the speed of 1 μm/min; Deposition time substrate temperature controls to be 800 ~ 900 DEG C, and it is 75 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into vacuum drying oven and heat-treats; Described Technology for Heating Processing is: vacuum degree control is 5 × 10
-2pa, heating rate is 3 DEG C/min, at 1050 DEG C, be incubated 4 hours, after stove cooling, can obtain NiCoCrAlY tack coat;
Carry out blasting treatment in the NiCoCrAlY tie layer surface prepared, its blasting craft is: angle is 90 degree, and distance is 200mm, and sand grains is 60 ~ 180 object emergies, and the time is 3 minutes, thus obtains desirable NiCoCrAlY surface;
With the NiCoCrAlY tack coat after blasting treatment for substrate, adopt electro beam physics vapour deposition technology to prepare ceramic top layer thereon, its concrete technology is: by Pr
2o
5powder is doped in zirconia, wherein Pr
2o
5the mass fraction of powder is 20%, after stirring, and is under the condition of 0.6MPa at pressure, sinters 10 hours, carry out high temperature insostatic pressing (HIP) at 1500 DEG C of temperature, forms the charge bar needed for electro beam physics vapour deposition, by the Pr of synthesis
2zr
2o
7be ceramic rod, put into electro beam physics vapour deposition vacuum chamber, by the vacuum degree control of vacuum chamber 2 × 10
-2pa, deposit with the speed of 0.5 μm/min, in order to obtain better bond strength and coating structure pattern, deposition time substrate temperature controls at about 850 DEG C, and coating layer thickness controls at about 80 μm, after the made sample got ready is cooled down, put into stove to heat-treat, its treatment process is: heating rate is 3 DEG C/min, is incubated 2 hours at 1050 DEG C, after stove cooling, namely can be made into required novel high temperature resistance thermal barrier coating.
Embodiment 3
The raw material configured is carried out high melt at 1500 ~ 1600 DEG C of temperature, is cast into NiCoCrAlY charge bar after melting, in described raw material, the mass fraction of Co is 24%, the mass fraction of Cr is 22%, the mass fraction of Al is the mass fraction of 10%, Y is 1.5%, and all the other are Ni; Being cast into the charge bar being of a size of Φ 68mm × 200mm after melting, gained NiCoCrAlY charge bar is put into electro beam physics vapour deposition vacuum chamber, is 10 × 10 by the vacuum degree control of vacuum chamber
-2pa, deposits with the speed of 2 μm/min; Deposition time substrate temperature controls to be 800 ~ 900 DEG C, and it is 90 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into vacuum drying oven and heat-treats; Described Technology for Heating Processing is: vacuum degree control is 10 × 10
-2pa, heating rate is 3 DEG C/min, at 1050 DEG C, be incubated 4 hours, after stove cooling, can obtain NiCoCrAlY tack coat;
Carry out blasting treatment in the NiCoCrAlY tie layer surface prepared, its blasting craft is: angle is 90 degree, and distance is 200mm, and sand grains is 60 ~ 180 object emergies, and the time is 3 minutes, thus obtains desirable NiCoCrAlY surface;
With the NiCoCrAlY tack coat after blasting treatment for substrate, adopt plasma spraying technology to prepare ceramic top layer thereon, its concrete technology is: by Pr
2o
5powder is doped in zirconia, wherein Pr
2o
5the mass fraction of powder is 30%, and the granularity of described Zirconium powder is 1 ~ 10 μm, and after stirring, adopt plasma spraying to be prepared into the thermal barrier coating that thickness is the novel high temperature resistance of about 120 μm, its concrete technique is as shown in the table:
Table 1 low-voltage plasma spraying prepares Pr
2zr
2o
7the technological parameter of the ceramic top layer that system is formed
| Voltage (v) | Electric current (A) | Argon flow amount (L/min) | Hydrogen flowing quantity (L/min) |
| 50 | 500 | 50 | 15 |
| Turntable rotating speed (turning/min) | Spray gun rotating speed (turning/min) | Cavity pressure (torr) | Powder feed rate (g/min) |
| 5 | 35 | 70 | 20 |
Claims (2)
1. a preparation method for lower thermal conductivity and high temperature heat-resistant barrier coating, is characterized in that, concrete steps are as follows:
(1) preparation of NiCoCrAlY tack coat, adopts one of following two schemes:
A. the technique adopting electro beam physics vapour deposition technology to prepare NiCoCrAlY tack coat is: the raw material configured is carried out high melt at 1500 ~ 1600 DEG C of temperature, NiCoCrAlY charge bar is cast into after melting, in described raw material, the mass fraction of Co is 22% ~ 24%, the mass fraction of Cr is 20% ~ 22%, the mass fraction of Al is 8% ~ 10%, the mass fraction of Y is 0.5% ~ 1.5%, and all the other are Ni; Gained NiCoCrAlY charge bar is put into electro beam physics vapour deposition vacuum chamber, is 1 × 10 by the vacuum degree control of vacuum chamber
-2~ 10 × 10
-2pa, deposits with the speed of 0.1 ~ 2 μm/min; Deposition time substrate temperature controls to be 800 ~ 900 DEG C, and it is 60 ~ 90 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into vacuum drying oven and heat-treats; Described Technology for Heating Processing is: vacuum degree control is 1 × 10
-2~ 10 × 10
-2pa, heating rate is 3 DEG C/min, at 1050 DEG C, be incubated 4 hours, after stove cooling, can obtain NiCoCrAlY tack coat;
B. the technological parameter adopting plasma spraying technology to prepare NiCoCrAlY tack coat is: voltage is 50 ~ 60V, electric current is 500 ~ 600A, argon flow amount is 50 ~ 60L/min, powder feeding rate is 20 ~ 40g/min, in the raw material used, the mass fraction of the mass fraction of Co to be the mass fraction of 22% ~ 24%, Cr be 20% ~ 22%, Al is 8% ~ 10%, the mass fraction of Y is 0.5% ~ 1.5%, and all the other are Ni;
(2) blasting treatment of NiCoCrAlY tack coat:
Carry out blasting treatment in the NiCoCrAlY tie layer surface prepared, its blasting craft is: angle is 90 degree, and distance is 200mm, and sand grains is 60 ~ 180 object emergies, and the time is 3 minutes;
(3) with the NiCoCrAlY tack coat after blasting treatment for substrate, prepare Pr thereon
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating, adopt one of following two schemes:
A. by Pr
2o
5powder is doped in zirconia, wherein Pr
2o
5the mass fraction of powder is 10% ~ 30%, after stirring, and is under the condition of 0.6MPa at pressure, 10 hours are sintered at 1500 DEG C of temperature, carry out high temperature insostatic pressing (HIP), obtain the charge bar needed for electro beam physics vapour deposition, then adopt electro beam physics vapour deposition to prepare Pr
2zr
2o
7ceramic top layer;
Described electro beam physics vapour deposition technique is: by the Pr of synthesis
2zr
2o
7charge bar, puts into electro beam physics vapour deposition vacuum chamber, is 1 × 10 by the vacuum degree control of vacuum chamber
-2~ 10 × 10
-2pa, deposits with the speed of 0.1 ~ 2 μm/min; During deposition, NiCoCrAlY tack coat base reservoir temperature controls is 800 ~ 900 DEG C, and it is 80 ~ 100 μm that coating layer thickness controls, and after being cooled down by the made sample got ready, puts into stove and heat-treats; Described Technology for Heating Processing is: heating rate is 3 DEG C/min, is incubated 2 hours at 1050 DEG C, after stove cooling, can prepare Pr
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating;
B. by Pr
2o
5be doped in Zirconium powder, wherein Pr
2o
5mass fraction be 10% ~ 30%, the granularity of described Zirconium powder is 1 ~ 10 μm, after stirring, and obtains the ceramic top layer powder needed for plasma spraying, adopt plasma spraying prepare Pr
2zr
2o
7ceramic top layer, thus obtain thermal barrier coating;
The technological parameter of described plasma spraying is: voltage is 50 ~ 60V, electric current is 500 ~ 600A, argon flow amount is 50 ~ 60L/min, hydrogen flowing quantity is 15 ~ 25L/min, turntable rotating speed is 5 ~ 15 turns/min, spray gun rotating speed is 35 ~ 45 turns/min, and cavity pressure is 70 torrs, and powder feeding rate is 20 ~ 40g/min.
2. preparation method according to claim 1, is characterized in that: in step (1), and described NiCoCrAlY charge bar is of a size of Φ 68mm × 200mm.
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|---|---|---|---|
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| CN103966539B (en) * | 2014-04-11 | 2016-08-17 | 北京航空航天大学 | A kind of plasma evaporation deposition long-life, the high heat insulation group of the lanthanides heat-barrier coating ceramic layer with composite construction and preparation method thereof |
| CN104674217B (en) * | 2015-03-09 | 2017-08-25 | 河南普莱姆涂层科技有限公司 | A kind of preparation method of the thermal barrier coating of the tack coat containing double-decker |
| CN107032831B (en) * | 2017-03-29 | 2018-02-23 | 北京航空航天大学 | A kind of Rare Earth T/EBC ceramic bases combinational environment barrier coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258467B1 (en) * | 2000-08-17 | 2001-07-10 | Siemens Westinghouse Power Corporation | Thermal barrier coating having high phase stability |
| US6294260B1 (en) * | 1999-09-10 | 2001-09-25 | Siemens Westinghouse Power Corporation | In-situ formation of multiphase air plasma sprayed barrier coatings for turbine components |
| CN102094170A (en) * | 2009-12-15 | 2011-06-15 | 沈阳天贺新材料开发有限公司 | Zirconium oxide thermal barrier coating for turbine buckets of gas turbine and preparation method thereof |
| CN102127738A (en) * | 2010-11-25 | 2011-07-20 | 北京航空航天大学 | Multilayer thermal barrier coating and preparation method thereof |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294260B1 (en) * | 1999-09-10 | 2001-09-25 | Siemens Westinghouse Power Corporation | In-situ formation of multiphase air plasma sprayed barrier coatings for turbine components |
| US6258467B1 (en) * | 2000-08-17 | 2001-07-10 | Siemens Westinghouse Power Corporation | Thermal barrier coating having high phase stability |
| CN102094170A (en) * | 2009-12-15 | 2011-06-15 | 沈阳天贺新材料开发有限公司 | Zirconium oxide thermal barrier coating for turbine buckets of gas turbine and preparation method thereof |
| CN102127738A (en) * | 2010-11-25 | 2011-07-20 | 北京航空航天大学 | Multilayer thermal barrier coating and preparation method thereof |
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