CN101948308A - Ceramic high-temperature insulation material - Google Patents
Ceramic high-temperature insulation material Download PDFInfo
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- CN101948308A CN101948308A CN 201010503224 CN201010503224A CN101948308A CN 101948308 A CN101948308 A CN 101948308A CN 201010503224 CN201010503224 CN 201010503224 CN 201010503224 A CN201010503224 A CN 201010503224A CN 101948308 A CN101948308 A CN 101948308A
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Abstract
The invention discloses a ceramic high-temperature insulation material. The material has a chemical formula of Sr1+w(A1-xB'yB''z)O3+delta, wherein A is Zr or Hf or a combination of the Zr or the Hf; B' is one or a combination of more than one of Ta, Nb, Ti or Sc; and B'' is La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Y and is one or a combination of more than one of Al, Cr, Co and Ni. A multi-metal oxide-modified perovskite structure ceramic material which has the characteristics of low thermal conductivity and high phase stability is obtained by codoping a plurality of metal oxides.
Description
Technical field:
The present invention relates to a kind of ceramic insulating material, particularly relate to a kind of ceramic high temperature lagging material with poly-metal deoxide modified perovskite structure of lower thermal conductivity, high phase stable.
Background technology:
For ground gas turbine and aero-gas turbine, must use the high temperature protection coating to protect its hot-end component, thereby improve the reliability of internal combustion turbine.Alloy coat can slow down the generation of hot-end component oxide on surface as anticorrosive, oxidation resistant coating under high temperature, aerobic and thermal cycle conditions, thereby prolongs the work-ing life of hot-end component.But the maximum operation (service) temperature of these alloy coats is lower than 1000 ℃.Thereby, even working under moderate temperature, internal combustion turbine also need a large amount of cooling gases to reduce the hot-end component temperature, this has reduced the performance and the efficient of internal combustion turbine significantly.
In order to improve the working temperature of internal combustion turbine hot-end component, thereby reduce the cooling gas consumption and improve gas turbine proficiency, the researchist has developed thermal barrier coating and it has been coated on internal combustion turbine hot-end component surface.Thermal barrier coating is a kind of thin ceramic layer, is used for air film refrigerative hot-end component and high-temperature fuel gas are kept apart, thereby helps to protect the internal combustion turbine hot-end component, and prolong its work-ing life.
The ceramic heat-barrier coating material that generally uses is 6～8wt.%Y at present
2O
3Partially stabilized ZrO
2(YSZ).YSZ has higher thermal expansivity (～11 * 10
-6K
-1), lower thermal conductivity (～2.1Wm
-1K
-1) and good thermal-shock resistance.But the life-time service temperature of YSZ is no more than 1200 ℃, and along with the further rising of temperature, serious structural instability appears in coating.On the one hand,, thereby cause coating thermal conductivity and Young's modulus to raise, make the strain tolerance limit of coating descend along with temperature rising YSZ coating generation sintering; On the other hand, in the thermal cycling process, the YSZ coating by metastable tetragonal phase converting be the four directions mutually with cube mutually, change the monocline phase then into, produce about 4% volume change, cause forming crackle in the coating, thereby destroyed the structural integrity of coating.
Along with improving constantly of internal combustion turbine working temperature, existing YSZ coating can not satisfy the design and use requirement of high-performance of future generation, low emission gas turbine.With the aero-turbine is example, and its development trend is to develop to high flow capacity ratio, high thrust-weight ratio direction, and the turbine engine inlet temperature further improves, thereby can improve motor efficiency greatly.The design inlet temperature that pushes away than 10 aircraft engines has reached more than 1577 ℃, and pushing away will be above 1727 ℃ than the design inlet temperature of the aircraft engine more than 15.Therefore, need to seek new ceramic heat-barrier coating material and replace existing YSZ.
Summary of the invention:
The object of the present invention is to provide a kind of ceramic high temperature lagging material with poly-metal deoxide modified perovskite structure of lower thermal conductivity, high phase stable.
Purpose of the present invention is implemented by following technical scheme, and a kind of ceramic high temperature lagging material, the chemical formula of compound are Sr
1+w(A
1-xB '
yB "
z) O
3+ δA is Zr or Hf, the perhaps combination of the two, B ' is a kind of among Ta, Nb, Ti or the Sc or more than one combination; B " be La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Y, and a kind of among Al, Cr, Co, the Ni or more than one combination ,-0.15≤w≤0.15 ,-0.15≤δ≤0.15,0.1≤x≤0.3, y+z=x, 0.02≤y≤0.15,0.02≤z≤0.15.
Described B ' is the one or any two kinds combination among Ta, Nb, Ti or the Sc.
Described B " be La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Y, and the one or any two kinds combination among Al, Cr, Co, the Ni.
Described compound has:
Sr (Zr
0.8Ta
0.1Yb
0.1) O
3Or Sr (Zr
0.9Sc
0.05Gd
0.05) O
2.95Or Sr (Hf
0.8Nb
0.1Dy
0.1) O
3Or Sr (Hf
0.9Sc
0.05Sm
0.05) O
2.95Or Sr (Hf
0.9Nb
0.05Nd
0.05) O
2.95Or Sr (Hf
0.8Ti
0.1Dy
0.1) O
2.95Or Sr (Hf
0.7Ta
0.15La
0.15) O
3Or Sr ((ZrHf)
0.9Ta
0.05Cr
0.05) O
3Or Sr (Hf
0.8(TaNb)
0.1Al
0.1) O
2.95Or Sr (Hf
0.7(TaTi)
0.15Ni
0.15) O
2.8875Or Sr (Hf
0.9(TaSc)
0.05Co
0.05) O
2.95Or Sr (Hf
0.8(NbSc)
0.1Cr
0.1) O
2.95Or Sr (Hf
0.7Nb
0.15(LaNd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaNd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(LaGd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaDy)
0.1) O
3Or Sr (Zr
0.8Ta
0.1(NdGd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(NdYb)
0.15) O
3Or Sr (Zr
0.7Ta
0.15(NdY)
0.15) O
3
When adopting air plasma spraying prepared coating, described compound S r
1+w(A
1-xB '
yB "
z) O
3+ δIn, the content of Sr is 0＜w≤0.15; When adopting electro beam physics vapour deposition prepared coating, described compound S r
1+w(A
1-xB '
yB "
z) O
3+ δIn, the content of Sr is-0.15≤w＜0.
Ceramic high temperature lagging material of the present invention can adopt the solid reaction process preparation.
Adopt solid reaction process to prepare above-mentioned ceramic high temperature lagging material, it comprises the steps:
(1) batching: with SrCO
3, the oxide compound of A, oxide compound and the B of B ' " oxide powder according to chemical formula Sr
1+w(A
1-xB '
yB "
z) O
3+ δMiddle positively charged ion mol ratio (1+w): (1-x): y: z mixes;
(2) ball milling: add the deionized water ball milling 12h-48h of 1-3 times of powder total mass, make slurry;
(3) drying: pour the slip behind the ball milling into container and be built in the loft drier at 80 ℃-120 ℃ following oven dry 6h-12h;
(4) thermal treatment: pour dried powder into corundum crucible at 1300 ℃-1600 ℃ heating 12h-48h;
(5) repeat (1)-(4) step until synthetic single-phase Sr
1+w(A
1-xB '
yB "
z) O
3+ δTill the powder, be generally one to three time.
The invention has the advantages that: the present invention obtains a kind of poly-metal deoxide modified perovskite structural ceramic material with lower thermal conductivity, high phase stable by the poly-metal deoxide codoped.By codoped, can suppress Sr (Zr/Hf) O effectively on the one hand
3Transformation mutually in room temperature to 1300 ℃ temperature range, thus reduce this material in the use temperature scope because Sr (Zr/Hf) O
3Undergo phase transition and cause the possibility of coating generation early failure, make this material in room temperature to 1450 ℃ temperature range, have good phase stability, and after 1450 ℃ of long term thermal are handled, have very high phase stability; On the other hand, can reduce Sr (Zr/Hf) O significantly
3Thermal conductivity, thereby improved the heat-proof quality of this material, the work-ing life that helps to improve coating system.Under the equal temperature condition, the thermal conductivity of co-doped material is than Sr (Zr/Hf) O
3Reduction more than 15%.
Description of drawings:
Fig. 1 is Sr (Zr among the embodiment 2
0.9Sc
0.05Gd
0.05) O
2.95With SrZrO
3Thermal conductivity numerical value comparison diagram under differing temps.
Fig. 2 is a thermal barrier coating system synoptic diagram in embodiment 1 or 3.
Fig. 3 is a thermal barrier coating system synoptic diagram in embodiment 2 or 4.
Embodiment:
Embodiment 1: adopt solid reaction process to prepare ceramic high temperature lagging material Sr (Zr
0.8Ta
0.1Yb
0.1) O
3, it comprises the steps:
(1) batching: with SrCO
3, ZrO
2, Ta
2O
5Oxide compound and Yb
2O
3Oxide powder by 1: 0.8: 0.05: 0.05 mixed in molar ratio;
(2) ball milling: add the deionized water ball milling 24h of 2 times of powder total masses, make slurry;
(3) drying: pour the slip behind the ball milling into container and be built in the loft drier at 100 ℃ of following oven dry 12h;
(4) thermal treatment: pour dried powder into corundum crucible at 1500 ℃ of heating 24h;
(5) repeat (1)-(4) step until synthetic single-phase Sr (Zr
0.8Ta
0.1Yb
0.1) O
3Till the powder, be generally one to three time.
This material has good phase stability under room temperature to 1400 ℃ and 1450 ℃ of long term thermal treatment condition, and the thermal conductivity under 1000 ℃ is 1.70Wm
-1K
-1, with SrZrO under the equal temperature condition
3Thermal conductivity (～2.10Wm
-1K
-1) compare and reduce by 19.0%.The gained powder is made the high workability powder through mist projection granulating.Adopt the vacuum plasma spray coating technology at the thick NiCrAlY metal bonding coating 2 of the about 100 μ m of nickel base superalloy matrix 3 surface deposition one decks, deposit the Sr (Zr of the about 300 μ m of a bed thickness then in NiCrAlY metal bonding coating 2 surface applications atmospheric plasma spraying technology
0.8Ta
0.1Yb
0.1) O
3 Ceramic layer 3 finally obtains thermal barrier coating system.
Embodiment 2: adopt embodiment 1 method to prepare ceramic high temperature lagging material Sr (Zr
0.9Sc
0.05Gd
0.05) O
2.95
This material has good phase stability under room temperature to 1400 ℃ and 1450 ℃ of long term thermal treatment condition, and the thermal conductivity under 1000 ℃ is 1.75Wm
-1K
-1, with SrZrO under the equal temperature condition
3Thermal conductivity (～2.10Wm
-1K
-1) compare and reduce by 16.7%.The gained powder is made the high workability powder through mist projection granulating.Adopt plating Pt to ooze Al technology at the thick PtAl metal bonding coating 3 of the about 80 μ m of nickel base superalloy matrix 4 surface preparation one decks, at first deposit the YSZ ceramic layer 2 of the about 150 μ m of a bed thickness then in PtAl metal bonding coating 3 surface applications atmospheric plasma spraying technology, deposit the Sr (Zr of the about 300 μ m of a bed thickness then on YSZ ceramic layer 2 surfaces again
0.9Sc
0.05Gd
0.05) O
2.95 Ceramic layer 1 finally obtains thermal barrier coating system.
Embodiment 3: adopt embodiment 1 method to prepare ceramic high temperature lagging material Sr (Hf
0.8Nb
0.1Dy
0.1) O
3This material has good phase stability under room temperature to 1400 ℃ and 1450 ℃ of long term thermal treatment condition, and the thermal conductivity under 1000 ℃ is 2.2Wm
-1K
-1, with SrHfO under the equal temperature condition
3Thermal conductivity (～2.70Wm
-1K
-1) compare and reduce by 22.7%.With the coldmoulding under the 60MPa condition of gained powder, green compact are put into retort furnace, insulation 2h when rising to 400 ℃ with 3 ℃/min temperature rise rate rises to 1200 ℃ of insulation 4h with 2 ℃/min temperature rise rate then, cools to room temperature then with the furnace and obtains being fit to the electro beam physics vapour deposition target.Adopt the electro beam physics vapour deposition technology at the thick NiCrAlY metal bonding coating 2 of the about 120 μ m of nickel base superalloy matrix 3 surface deposition one decks, adopt the electro beam physics vapour deposition technology to deposit the Sr (Hf of the about 300 μ m of a bed thickness in tie layer surface then
0.8Nb
0.1Dy
0.1) O
3 Ceramic layer 1 finally obtains thermal barrier coating system.
Embodiment 4: adopt embodiment 1 method to prepare ceramic high temperature lagging material Sr (Hf
0.9Sc
0.05Sm
0.05) O
2.95This material has good phase stability under room temperature to 1400 ℃ and 1450 ℃ of long term thermal treatment condition, and the thermal conductivity under 1000 ℃ is 2.0Wm
-1K
-1, with SrHfO under the equal temperature condition
3Thermal conductivity (～2.70Wm
-1K
-1) compare and reduce by 25.9%.With the coldmoulding under the 50MPa condition of gained powder, green compact are put into retort furnace, insulation 3h when rising to 500 ℃ with 5 ℃/min temperature rise rate rises to 1300 ℃ of insulation 6h with 1 ℃/min temperature rise rate then, cools to room temperature then with the furnace and obtains being fit to the electro beam physics vapour deposition target.Adopt the electro beam physics vapour deposition technology at the thick NiCoCrAlY metal bonding coating 3 of the about 80 μ m of nickel base superalloy matrix 4 surface deposition one decks, adopt the electro beam physics vapour deposition technology at first to deposit the YSZ ceramic layer 2 of the about 170 μ m of a bed thickness then, adopt the electro beam physics vapour deposition technology to deposit the Sr (Hf of the about 280 μ m of a bed thickness again on YSZ ceramic layer 2 surfaces then in tie layer surface
0.9Sc
0.05Sm
0.05) O
2.95 Ceramic layer 1 finally obtains thermal barrier coating system.
Embodiment 5: adopt embodiment 1 or embodiment 2 methods to prepare ceramic high temperature lagging material Sr (Hf
0.9Nb
0.05Nd
0.05) O
2.95Or Sr (Hf
0.8Ti
0.1Dy
0.1) O
2.95Or Sr (Hf
0.7Ta
0.15La
0.15) O
3Or Sr ((ZrHf)
0.9Ta
0.05Cr
0.05) O
3Or Sr (Hf
0.8(TaNb)
0.1Al
0.1) O
2.95Or Sr (Hf
0.7(TaTi)
0.15Ni
0.15) O
2.8875Or Sr (Hf
0.9(TaSc)
0.05Co
0.05) O
2.25Or Sr (Hf
0.8(NbSc)
0.1Cr
0.1) O
2.95Or Sr (Hf
0.7Nb
0.15(LaNd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaNd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(LaGd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaDy)
0.1) O
3Or Sr (Zr
0.8Ta
0.1(NdGd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(NdYb)
0.15) O
3Or Sr (Zr
0.7Ta
0.15(NdY)
0.15) O
3The above material that obtains has good phase stability in room temperature to 1450 ℃ temperature range, and has very high phase stability after 1450 ℃ of long term thermal are handled; And the thermal conductivity under 1000 ℃ is all than Sr (Zr/Hf) O
3Thermal conductivity reduce more than 15%.
Claims (5)
1. ceramic high temperature lagging material, it is characterized in that: the chemical formula of compound is Sr
1+w(A
1-xB '
yB "
z) O
3+ δA is Zr or Hf, the perhaps combination of the two, B ' is a kind of among Ta, Nb, Ti or the Sc or more than one combination; B " be La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Y, and a kind of among Al, Cr, Co, the Ni or more than one combination ,-0.15≤w≤0.15 ,-0.15≤δ≤0.15,0.1≤x≤0.3, y+z=x, 0.02≤y≤0.15,0.02≤z≤0.15.
2. a kind of ceramic high temperature lagging material according to claim 1 is characterized in that: described B ' is the one or any two kinds combination among Ta, Nb, Ti or the Sc.
3. a kind of ceramic high temperature lagging material according to claim 1 is characterized in that: described B " be La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu, Y, and the one or any two kinds combination among Al, Cr, Co, the Ni.
4. a kind of ceramic high temperature lagging material according to claim 1 is characterized in that described compound has:
Sr (Zr
0.8Ta
0.1Yb
0.1) O
3Or Sr (Zr
0.9Sc
0.05Gd
0.05) O
2.95Or Sr (Hf
0.8Nb
0.1Dy
0.1) O
3Or Sr (Hf
0.9Sc
0.05Sm
0.05) O
2.95Or Sr (Hf
0.9Nb
0.05Nd
0.05) O
2.95Or Sr (Hf
0.8Ti
0.1Dy
0.1) O
2.95Or Sr (Hf
0.7Ta
0.15La
0.15) O
3Or Sr ((ZrHf)
0.9Ta
0.05Cr
0.05) O
3Or Sr (Hf
0.8(TaNb)
0.1Al
0.1) O
2.29Or Sr (Hf
0.7(TaTi)
0.15Ni
0.15) O
2.8875Or Sr (Hf
0.9(TaSc)
0.05Co
0.05) O
2.95Or Sr (Hf
0.8(NbSc)
0.1Cr
0.1) O
2.95Or Sr (Hf
0.7Nb
0.15(LaNd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaNd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(LaGd)
0.15) O
3Or Sr (Hf
0.8Ta
0.1(LaDy)
0.1) O
3Or Sr (Zr
0.8Ta
0.1(NdGd)
0.1) O
3Or Sr (Hf
0.7Ta
0.15(NdYb)
0.15) O
3Or Sr (Zr
0.7Ta
0.15(NdY)
0.15) O
3
5. a kind of ceramic high temperature lagging material according to claim 1 is characterized in that: when adopting air plasma spraying prepared coating, and described compound S r
1+w(A
1-xB '
yB "
z) O
3+ δIn, the content of Sr is 0＜w≤0.15; When adopting electro beam physics vapour deposition prepared coating, described compound S r
1+w(A
1-xB '
yB "
z) O
3+ δIn, the content of Sr is-0.15≤w＜0.
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|---|---|---|---|
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|---|---|---|---|
| CN 201010503224 CN101948308B (en) | 2010-09-27 | 2010-09-27 | Ceramic high-temperature insulation material |
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| CN101948308A true CN101948308A (en) | 2011-01-19 |
| CN101948308B CN101948308B (en) | 2013-01-02 |
Family
ID=43451958
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Cited By (6)
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|---|---|---|---|---|
| CN102674893A (en) * | 2012-05-31 | 2012-09-19 | 西北有色金属研究院 | Ultrahigh-temperature antioxidant coating for carbon/carbon composite material and preparation method of ultrahigh-temperature antioxidant coating |
| CN102786303A (en) * | 2012-08-07 | 2012-11-21 | 内蒙古工业大学 | Ceramic nanometer composite material for heat barrier coating and preparation method of ceramic nanometer composite material |
| WO2013053727A1 (en) * | 2011-10-12 | 2013-04-18 | Areva | Electrode for electrochemical cell and method of manufacturing such an electrode |
| CN111348924A (en) * | 2018-12-20 | 2020-06-30 | 攀枝花学院 | Refractory and corrosion-resistant material for resisting titanium melt and preparation method and application thereof |
| CN111960823A (en) * | 2020-08-28 | 2020-11-20 | 昆明理工大学 | Alkaline earth metal ion doped rare earth tantalate or niobate thermal barrier coating and preparation method thereof |
| CN113845911A (en) * | 2020-12-04 | 2021-12-28 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
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Cited By (8)
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|---|---|---|---|---|
| WO2013053727A1 (en) * | 2011-10-12 | 2013-04-18 | Areva | Electrode for electrochemical cell and method of manufacturing such an electrode |
| FR2981508A1 (en) * | 2011-10-12 | 2013-04-19 | Areva | ELECTRODE FOR ELECTROCHEMICAL CELL AND METHOD FOR MANUFACTURING SUCH ELECTRODE |
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| CN102674893A (en) * | 2012-05-31 | 2012-09-19 | 西北有色金属研究院 | Ultrahigh-temperature antioxidant coating for carbon/carbon composite material and preparation method of ultrahigh-temperature antioxidant coating |
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| CN111348924A (en) * | 2018-12-20 | 2020-06-30 | 攀枝花学院 | Refractory and corrosion-resistant material for resisting titanium melt and preparation method and application thereof |
| CN111960823A (en) * | 2020-08-28 | 2020-11-20 | 昆明理工大学 | Alkaline earth metal ion doped rare earth tantalate or niobate thermal barrier coating and preparation method thereof |
| CN113845911A (en) * | 2020-12-04 | 2021-12-28 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
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| Publication number | Publication date |
|---|---|
| CN101948308B (en) | 2013-01-02 |
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