CN106567077A - Preparation method of thermal barrier coating on surface of high temperature alloy - Google Patents
Preparation method of thermal barrier coating on surface of high temperature alloy Download PDFInfo
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- CN106567077A CN106567077A CN201611004540.2A CN201611004540A CN106567077A CN 106567077 A CN106567077 A CN 106567077A CN 201611004540 A CN201611004540 A CN 201611004540A CN 106567077 A CN106567077 A CN 106567077A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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Abstract
The invention discloses a preparation method of a thermal barrier coating on the surface of a high temperature alloy. The preparation method comprises the steps of firstly, preparing nano zirconium acid-rolled ceramic powder; then, after carrying out pre-grinding, polishing and cleaning on a high temperature alloy matrix, depositing a bonding layer on the high temperature alloy matrix through the low pressure plasma spraying method; then, spraying a ceramic protective layer on the surface of the bonding layer through the plasma spraying technology; finally, depositing a nano Gd2Zr2O7 ceramic layer on the ceramic protective layer as the thermal barrier coating through the electron beam physical vapor deposition method; and then, removing dust and particles on the surface of the prepared ceramic thermal barrier coating through a vacuum dust collector, and putting the thermal barrier coating into an oven to be dried. According to the prepared thermal barrier coating, thermal conductivity is low, high temperature resistance of the alloy can be effectively improved, and the thermal barrier coating is compact in structure, not liable to crack, and good in oxidation resistance and corrosion resistance.
Description
Technical field：
The present invention relates to metal surface modification field, is specifically related to a kind of preparation side of high-temp. alloy surface heat barrier
Method.
Background technology：
Now, the main development direction of gas-turbine unit is to improve ignition temperature before engine turbine, increase to have an high regard for
Than and lift turbine engine components and including corrosion and the thermal efficiency under harsh Service Environment such as aoxidizing.With engine combustion
The raising of temperature, thrust-weight ratio and the thermal efficiency, the fuel gas temperature and gaseous-pressure in engine thermal end pieces, particularly combustor is not
It is disconnected to improve.The end from last century forties the to last century, gaseous-pressure ratio improves nearly 3 times, and fuel gas temperature is more than 1650 DEG C.For
Reach raising efficiency, the requirement of energy saving, the operating temperature of combustion gas turbine almost with the speed of 15 DEG C/a it is quick on
Rise, it is contemplated that be up to 1930 DEG C quickly.So high temperature alreadys exceed the fusing point of existing alloy, and novel high-temperature alloy is heat-resisting
The growth of performance only about 5 DEG C/a, therefore, it is necessary to using corresponding measure.On the one hand, using vacuum melting and hot investment casting
Etc. advanced technology of preparing and continue the high-temperature material of development of new, improve the heat resistance of high temperature alloy, such as directional solidification is closed
Gold and single crystal alloy；On the other hand, using advanced cooling technology, the such as design of blade cooling air film and the improvement of manufacturing process.
Yet with being limited by its fusing point, the potentiality for further improving high temperature alloy operating temperature are extremely limited.Cause
Power while further Development of Novel alloy and cooling technology, expect to seek other approach by engine designers, to reduce
The failure that the service temperature and reduction engine blade of high temperature alloy causes because overheated, wherein development high-temp heat barrier coating technology
Yearning, with development prospect.
Thermal barrier coating is by ceramic oxide surface layer and plays the heat-protection system that the priming coat of cementation is constituted.It is using pottery
The excellent high temperature resistant of ceramic material, resistance to erosion, anticorrosive and low heat conductivity energy, improve the allowable work temperature of metal parts, strengthen
The high-temperature resistance of hot-end component, extends the service life of hot-end component, improves the work efficiency of electromotor.Therefore how to be obtained
Fine and close, antioxygenic property is good, low thermal conductivity thermal barrier coating becomes the key for improving high temperature alloy heat resistance.
The content of the invention：
It is an object of the invention to provide a kind of preparation method of high-temp. alloy surface heat barrier, the method is simple to operate,
Low for equipment requirements, obtained thermal barrier coating low thermal conductivity, good stability can effectively improve the resistance to elevated temperatures and antioxygen of alloy
Change performance.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs；
B) weak ammonia is taken, will be dropwise instilled in the weak ammonia of stirring containing Gd and Zr mixed solutions with peristaltic pump, completion of dropping
Afterwards, stirring, ageing are closed；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 20-24h at 180-200 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, it is dried at 50-70 DEG C, drying
Grinding after complete, and sieve in 200 eye mesh screens, subsequently in Muffle kiln roasting, obtain Gd2Zr2O7Nano-powder；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after with graphite jig together in drying baker be dried, subsequently on desk type powder dry press
Precompressed, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 60-80MPa, set program power and
Time, start sintering, sintering is finished, treat that in-furnace temperature is down to less than 30 DEG C, start release, treat that whole pressure are unsnatched, deflate, open
Fire door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
Tack coat is deposited on high temperature alloy matrix, then using plasma spray coating process in the ceramic coated protective layer of tie layer surface；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Nanometer Gd is deposited on ceramic protective layer using electro beam physics vapour deposition method2Zr2O7Ceramic layer is used as thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Used as the preferred of above-mentioned technical proposal, in step a), laboratory temperature is 5-20 DEG C.
Used as the preferred of above-mentioned technical proposal, in step b), the concentration of the mixed solution containing Gd and Zr is 0.03-
0.05mol/L, the concentration of weak ammonia is 0.4-0.6mol/L, and weak ammonia is 2 with the volume ratio of the mixed solution containing Gd and Zr:1.
Used as the preferred of above-mentioned technical proposal, in step b), the time of the ageing is 20-24h.
Used as the preferred of above-mentioned technical proposal, in step d), the temperature of the roasting is 800-1000 DEG C, the time of roasting
For 2-5h.
Used as the preferred of above-mentioned technical proposal, in step e), the temperature of the drying is 180-200 DEG C, the dry time
For 4-6h.
As the preferred of above-mentioned technical proposal, in step f), during sintering, first with the ramp of 30-40 DEG C/min extremely
600 DEG C, then with the ramp of 40-60 DEG C/min to 1300-1350 DEG C, 3-5min is incubated, subsequently presses 30-50 DEG C/min drops
To 600 DEG C, sintering is finished temperature.
Used as the preferred of above-mentioned technical proposal, in step (2), the tack coat is NiCrAlY, and its thickness is 0.05-
0.08mm。
Used as the preferred of above-mentioned technical proposal, in step (2), the protective layer is aluminium oxide, titanium oxide, silicon oxide, oxygen
Change the complex of one or more composition in zirconium, the thickness of protective layer is 0.001-0.002mm.
Used as the preferred of above-mentioned technical proposal, in step (3), the thickness of the thermal barrier coating is 0.07-0.12mm.
Compared with prior art, the invention has the advantages that：
The present invention sprays successively tack coat, ceramic protective layer and thermal barrier coating in high-temperature alloy surface, ties between layers
With joint efforts well, it is difficult for drop-off, the heat resistance and stability of the high temperature alloy that can be effectively improved；
The present invention is modified to nano-powder, obtained nanometer Gd2Zr2O7Ceramic powder size is little, better crystallinity degree, point
Scattered property is good, and obtained thermal barrier coating compactness is good, not easy to crack, low thermal conductivity, can effectively improve the resistance to elevated temperatures of alloy, and
The preparation method time is short, efficiency high, energy saving.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs, and obtains concentration containing for 0.03mol/L
Gd and Zr mixed solutions；
B) weak ammonia that concentration is 0.4mol/L is taken, the dilute of stirring will be dropwise instilled containing Gd and Zr mixed solutions with peristaltic pump
In ammonia, after completion of dropping, stirring is closed, be aged 20h, wherein, weak ammonia is with the volume ratio of the mixed solution containing Gd and Zr
2:1；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 20h at 180 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying, has been dried at 50 DEG C
After grind, and sieve in 200 eye mesh screens, subsequently in Muffle furnace, roasting 2h, obtains Gd at 800 DEG C2Zr2O7Nano powder
Body；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after be dried 4h at 180 DEG C in drying baker together with graphite jig, subsequently in desk type powder
Precompressed on dry press, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 60MPa, set program power and when
Between, start sintering, during sintering, first with the ramp of 30 DEG C/min to 600 DEG C, then with the ramp of 40 DEG C/min extremely
1300 DEG C, 3min is incubated, subsequently cools to 600 DEG C by 30 DEG C/min, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, is opened
Beginning release, treats that whole pressure are unsnatched, and deflates, and blow-on door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
The NiCrAlY tack coats that thickness is 0.05mm are deposited as on high temperature alloy matrix, then using plasma spray coating process viscous
Knot layer surface coating thickness is the ceramic protective layer of 0.001mm；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Using electro beam physics vapour deposition method, deposit thickness is nanometer Gd of 0.07mm on ceramic protective layer2Zr2O7Ceramic layer is made
For thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Embodiment 2
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs, and obtains concentration containing for 0.05mol/L
Gd and Zr mixed solutions；
B) weak ammonia that concentration is 0.6mol/L is taken, the dilute of stirring will be dropwise instilled containing Gd and Zr mixed solutions with peristaltic pump
In ammonia, after completion of dropping, stirring is closed, be aged 24h, wherein, weak ammonia is with the volume ratio of the mixed solution containing Gd and Zr
2:1；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 24h at 200 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying, has been dried at 70 DEG C
After grind, and sieve in 200 eye mesh screens, subsequently in Muffle furnace, roasting 5h, obtains Gd at 1000 DEG C2Zr2O7Nano powder
Body；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after be dried 6h at 200 DEG C in drying baker together with graphite jig, subsequently in desk type powder
Precompressed on dry press, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 80MPa, set program power and when
Between, start sintering, during sintering, first with the ramp of 40 DEG C/min to 600 DEG C, then with the ramp of 60 DEG C/min extremely
1350 DEG C, 5min is incubated, subsequently cools to 600 DEG C by 50 DEG C/min, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, is opened
Beginning release, treats that whole pressure are unsnatched, and deflates, and blow-on door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
The NiCrAlY tack coats that thickness is 0.08mm are deposited as on high temperature alloy matrix, then using plasma spray coating process viscous
Knot layer surface coating thickness is the ceramic protective layer of 0.002mm；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Using electro beam physics vapour deposition method, deposit thickness is nanometer Gd of 0.12mm on ceramic protective layer2Zr2O7Ceramic layer is made
For thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Embodiment 3
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs, and obtains concentration for 0.035mol/L's
Containing Gd and Zr mixed solutions；
B) weak ammonia that concentration is 0.45mol/L is taken, stirring will be dropwise instilled containing Gd and Zr mixed solutions with peristaltic pump
In weak ammonia, after completion of dropping, stirring is closed, be aged 21h, wherein, the volume ratio of weak ammonia and the mixed solution containing Gd and Zr
For 2:1；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 21h at 185 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying, has been dried at 55 DEG C
After grind, and sieve in 200 eye mesh screens, subsequently in Muffle furnace, roasting 3h, obtains Gd at 850 DEG C2Zr2O7Nano powder
Body；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after be dried 4.5h at 185 DEG C in drying baker together with graphite jig, subsequently in desk-top powder
Precompressed on last dry press, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 65MPa, set program power and when
Between, start sintering, during sintering, first with the ramp of 33 DEG C/min to 600 DEG C, then with the ramp of 45 DEG C/min extremely
1310 DEG C, 3min is incubated, subsequently cools to 600 DEG C by 35 DEG C/min, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, is opened
Beginning release, treats that whole pressure are unsnatched, and deflates, and blow-on door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
The NiCrAlY tack coats that thickness is 0.06mm are deposited as on high temperature alloy matrix, then using plasma spray coating process viscous
Knot layer surface coating thickness is the ceramic protective layer of 0.001mm；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Using electro beam physics vapour deposition method, deposit thickness is nanometer Gd of 0.08mm on ceramic protective layer2Zr2O7Ceramic layer is made
For thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Embodiment 4
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs, and obtains concentration containing for 0.04mol/L
Gd and Zr mixed solutions；
B) weak ammonia that concentration is 0.5mol/L is taken, the dilute of stirring will be dropwise instilled containing Gd and Zr mixed solutions with peristaltic pump
In ammonia, after completion of dropping, stirring is closed, be aged 22h, wherein, weak ammonia is with the volume ratio of the mixed solution containing Gd and Zr
2:1；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 22h at 190 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying, has been dried at 60 DEG C
After grind, and sieve in 200 eye mesh screens, subsequently in Muffle furnace, roasting 4h, obtains Gd at 900 DEG C2Zr2O7Nano powder
Body；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after be dried 5h at 190 DEG C in drying baker together with graphite jig, subsequently in desk type powder
Precompressed on dry press, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 70MPa, set program power and when
Between, start sintering, during sintering, first with the ramp of 36 DEG C/min to 600 DEG C, then with the ramp of 50 DEG C/min extremely
1320 DEG C, 4min is incubated, subsequently cools to 600 DEG C by 40 DEG C/min, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, is opened
Beginning release, treats that whole pressure are unsnatched, and deflates, and blow-on door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
The NiCrAlY tack coats that thickness is 0.07mm are deposited as on high temperature alloy matrix, then using plasma spray coating process viscous
Knot layer surface coating thickness is the ceramic protective layer of 0.001mm；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Using electro beam physics vapour deposition method, deposit thickness is nanometer Gd of 0.09mm on ceramic protective layer2Zr2O7Ceramic layer is made
For thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Embodiment 5
A kind of preparation method of high-temp. alloy surface heat barrier, comprises the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs, and obtains concentration for 0.045mol/L's
Containing Gd and Zr mixed solutions；
B) weak ammonia that concentration is 0.55mol/L is taken, stirring will be dropwise instilled containing Gd and Zr mixed solutions with peristaltic pump
In weak ammonia, after completion of dropping, stirring is closed, be aged 23h, wherein, the volume ratio of weak ammonia and the mixed solution containing Gd and Zr
For 2:1；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after
In the supernatant without white precipitate till, then again with washes of absolute alcohol 2-3 time；Finally by the anhydrous second of the precipitation after washing
It is put in reactor after alcohol dilution and reacts 23h at 195 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying, has been dried at 65 DEG C
After grind, and sieve in 200 eye mesh screens, subsequently in Muffle furnace, roasting 4h, obtains Gd at 950 DEG C2Zr2O7Nano powder
Body；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, and sleeve lining and upper push-down head are respectively padded
One layer of carbon paper, by nano-powder it is die-filling after be dried 5.5h at 195 DEG C in drying baker together with graphite jig, subsequently in desk-top powder
Precompressed on last dry press, preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, is closed in discharge plasma sintering furnace
Closed furnace door starts evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 75MPa, set program power and when
Between, start sintering, during sintering, first with the ramp of 38 DEG C/min to 600 DEG C, then with the ramp of 55 DEG C/min extremely
1340 DEG C, 4min is incubated, subsequently cools to 600 DEG C by 45 DEG C/min, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, is opened
Beginning release, treats that whole pressure are unsnatched, and deflates, and blow-on door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed
The NiCrAlY tack coats that thickness is 0.07mm are deposited as on high temperature alloy matrix, then using plasma spray coating process viscous
Knot layer surface coating thickness is the ceramic protective layer of 0.002mm；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer under nitrogen or argon
Cleaned using pulse laser；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally
Using electro beam physics vapour deposition method, deposit thickness is nanometer Gd of 0.10mm on ceramic protective layer2Zr2O7Ceramic layer is made
For thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put
Enter in baking oven and be dried.
Claims (10)
1. a kind of preparation method of high-temp. alloy surface heat barrier, it is characterised in that comprise the following steps：
(1) preparation of nanometer zirconic acid gadolinium ceramic powder：
A) laboratory temperature is adjusted with air-conditioning, according to Gd：Zr mol ratios are 1:1 weighs respectively Gd (NO3)3·6H2O and
ZrOCl2·8H2O, plus deionized water is diluted to the mixed solution containing Gd and Zr, stirs；
B) weak ammonia is taken, will be dropwise instilled in the weak ammonia of stirring containing Gd and Zr mixed solutions with peristaltic pump, after completion of dropping, closed
Stirring is closed, is aged；
C) precipitation after ageing is carried out into centrifuge washing, be first washed with deionized to by silver nitrate be added to centrifugation after upper strata
In clear liquid without white precipitate till, then again with washes of absolute alcohol 2-3 time；It is finally that the precipitation after washing is dilute with dehydrated alcohol
It is put into after releasing in reactor and reacts 20-24h at 180-200 DEG C；
D) by precipitation absolute ethanol washing 1-2 time after reaction terminates, in being put into drying baker, drying at 50-70 DEG C, after being dried
Grinding, and sieve in 200 eye mesh screens, subsequently in Muffle kiln roasting, obtain Gd2Zr2O7Nano-powder；
E) Gd obtained in step d) is taken2Zr2O7Nano-powder is placed in graphite jig, one layer of sleeve lining and each pad of upper push-down head
Carbon paper, by nano-powder it is die-filling after with graphite jig together in drying baker be dried, the subsequently precompressed on desk type powder dry press,
Preload pressure is 1-2MPa；
F) will be equipped with Gd2Zr2O7The graphite jig of nano-powder after correct placement, closes stove in discharge plasma sintering furnace
Door start evacuation, whne vacuum be less than 6Pa when, start pressurization, pressure is 60-80MPa, set program power and when
Between, starting sintering, sintering is finished, and treats that in-furnace temperature is down to less than 30 DEG C, starts release, treats that whole pressure are unsnatched, and is deflated, blow-on
Door, the demoulding, sampling, attrition grinding obtains a nanometer Gd2Zr2O7Ceramic powder；
(2) by high temperature alloy matrix after pre-grinding, polishing, cleaning treatment, using the method for Low Pressure Condition Plasma Sprayed in height
Temperature alloy substrate deposit tack coat, then using plasma spray coating process in the ceramic coated protective layer of tie layer surface；
(3) and then by the high temperature alloy matrix surface for being coated with tack coat and ceramic protective layer adopt under nitrogen or argon
Pulse laser is cleaned；And the material surface after cleaning is carried out into laser roughening process under vacuum or argon protection, finally utilize
Electro beam physics vapour deposition method deposits nanometer Gd on ceramic protective layer2Zr2O7Ceramic layer is used as thermal barrier coating；
(4) surface dust and granule are removed with vacuum cleaner to ceramic heat-barrier coating surface obtained in step (3), and is put into baking
It is dried in case.
2. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step a)
In, laboratory temperature is 5-20 DEG C.
3. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step b)
In, the concentration of the mixed solution containing Gd and Zr is 0.03-0.05mol/L, and the concentration of weak ammonia is 0.4-0.6mol/L, dilute
Ammonia is 2 with the volume ratio of the mixed solution containing Gd and Zr:1.
4. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step b)
In, the time of the ageing is 20-24h.
5. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step d)
In, the temperature of the roasting is 800-1000 DEG C, and the time of roasting is 2-5h.
6. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step e)
In, the temperature of the drying is 180-200 DEG C, and the dry time is 4-6h.
7. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step f)
In, during sintering, first with the ramp of 30-40 DEG C/min to 600 DEG C, then with the ramp of 40-60 DEG C/min extremely
1300-1350 DEG C, 3-5min is incubated, subsequently cools to 600 DEG C by 30-50 DEG C/min, sintering is finished.
8. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step (2)
In, the tack coat is NiCrAlY, and its thickness is 0.05-0.08mm.
9. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step (2)
In, the protective layer is the complex of one or more composition in aluminium oxide, titanium oxide, silicon oxide, zirconium oxide, protective layer
Thickness is 0.001-0.002mm.
10. a kind of preparation method of high-temp. alloy surface heat barrier as claimed in claim 1, it is characterised in that：Step (3)
In, the thickness of the thermal barrier coating is 0.07-0.12mm.
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