CN114059066A - 一种用于提高基于铂铝粘结层的热障涂层寿命的方法 - Google Patents
一种用于提高基于铂铝粘结层的热障涂层寿命的方法 Download PDFInfo
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- 239000012720 thermal barrier coating Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 57
- 230000003647 oxidation Effects 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001011 CMSX-4 Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000011253 protective coating Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 11
- 238000005382 thermal cycling Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005524 ceramic coating Methods 0.000 description 3
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- XSBJUSIOTXTIPN-UHFFFAOYSA-N aluminum platinum Chemical compound [Al].[Pt] XSBJUSIOTXTIPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
本发明公开了一种用于提高基于铂铝粘结层的热障涂层寿命的方法,属于高温防护涂层技术领域。本发明通过预氧化的方法,预先在铂铝涂层表面制备一层TGO氧化膜,作为TBC涂层的底层粘结层。铂铝涂层粘结层主要依靠表面生成氧化膜TGO来与TBCs热障涂层顶层YSZ粘结,TGO氧化膜的厚度增加由于O与Al原子扩散速率的原因呈现抛物线型生长模式,当TGO厚度增加产生的应力集中导致TGO本身开裂脱落,会导致TBC涂层失效。由于低压预氧化工艺可以预先在铂铝粘结层表面生成一层致密氧化膜TGO,减缓TGO的生长速度,因此可以改善TBCs热障涂层的寿命。
Description
技术领域
本发明涉及高温防护涂层技术领域,具体涉及一种用于提高基于铂铝粘结层的热障涂层寿命的方法。
背景技术
作为一种具有良好抗氧化、抗热腐蚀性能的铂改性铝化物涂层,已被广泛应用于航空发动机、燃气轮机叶片等耐热部件的防护,它既可以单独使用,也可以作为粘接层(bond coat)与表面陶瓷层(如Y2O3稳定ZrO2)一起构成热障涂层(TBCs,即thermal barriercoatings)体系,来提高部件的抗高温氧化、抗热腐蚀性能,延长部件的服役寿命。相关应用的文献如:①中国发明专利,Pt+Si改性的β-NiAl热障涂层极其制备方法,申请号201210078703.7;②中国发明专利,用于隔热涂层的经铂改性的NiCoCrAlY结合涂层,申请号20061016095.5;③中国发明专利,一种防护涂层,申请号200410003852.2。
对于高温合金及高温防护涂层部件而言,其抗氧化性能主要依靠:(1)一层致密并且生长缓慢的Al2O3膜(TGO),阻止元素的内外扩散;以及(2)氧化钇稳定氧化锆陶瓷涂层来降低粘结层表面的温度。但是由于Al2O3膜和陶瓷涂层很脆,粘结层涂层在使用过程当中Al2O3膜(TGO)厚度增加导致的应力集中很容易导致Al2O3膜和陶瓷涂层脱落,因此如能抑制Al2O3膜(TGO)的生长则可以提高TBCs涂层的使用寿命。
发明内容
为了进一步提高铂铝粘结层在TBCs中的服役时间,本发明提供一种用于提高基于铂铝粘结层的热障涂层寿命的方法,该方法采用低压氧化的手段在铂铝涂层表面生成一层致密的氧化铝薄膜,延缓铂铝涂层在高温氧化中TGO的生长速度,该方法提高了TBCs涂层的使用寿命。
为实现上述目的,本发明所采用的技术方案如下:
一种用于提高基于铂铝粘结层的热障涂层寿命的方法,该方法首先在基体表面制备铂铝涂层,然后采用低压预氧化工艺在铂铝涂层表面形成一层致密TGO获得铂铝粘结层,最后在所述TGO上面制备YSZ氧化钇改性氧化锆涂层。
所述基体为CMSX-4、DD419、Rene5或DD5合金。
所述铂铝涂层化学成分为:Pt为10-40wt%,Al为20-40wt%,Ni为30-40wt%;所述铂铝涂层中β-(Ni,Pt)Al为主相。
所述铂铝涂层厚度为20~60μm。
所述低压预氧化工艺是指采用氧气对基体上的铂铝涂层进行处理,其中:处理压力为1×10-2~1×103Pa,处理温度为900~1080℃,处理时间为3~8h,通入浓度≥99.99%纯氧,通入纯氧流量为1~300ml/min。所述低压预氧化工艺中,在真空条件下加热,达到处理温度900℃-1080℃后通入氧气,保温结束后停止通入气体,在真空条件下炉冷到100℃以下取样。
所述铂铝涂层采用低压预氧化工艺处理后,铂铝涂层表面生成一层TGO氧化膜(主要为α-Al2O3膜),TGO氧化膜厚度为0.5~4μm。生成TGO氧化膜的表面粗糙度为Ra=0.5~1.6。
所述YSZ氧化钇改性氧化锆涂层的厚度为80~250μm。
本发明的优点和有益效果如下:
1、本发明通过低压预氧化处理在铂铝涂层表面预先生成一层很薄的致密的Al2O3膜(TGO),进而可以抑制Al2O3膜中O和Al的互扩散,降低生长速率,延长TBCs热障涂层服役时间。
2、铂铝涂层主要依靠表面生成氧化膜TGO与TBCs热障涂层顶层YSZ粘结,TGO氧化膜的厚度增加由于O与Al原子扩散速率的原因呈现抛物线型生长模式,当TGO厚度增加产生的应力集中导致TGO本身开裂脱落,会导致TBC涂层失效。本发明采用低压预氧化工艺可以预先在铂铝涂层表面生成一层致密氧化膜TGO(主要为α-Al2O3膜),通过消耗一部分β-(Ni,Pt)Al相在表面形成致密的氧化铝薄膜,减缓TGO的生长速度,因此可以提高TBCs热障涂层的寿命。
3、单纯的铂铝涂层在进行高温氧化时,氧化膜中多数为致密性较差的θ-Al2O3,而进行预氧化后,铂铝粘结层表面生成一层致密的α-Al2O3,可减缓涂层进一步的氧化,降低氧化速率。因此预氧化可以有效的提高的铂铝粘结层TBCs的寿命。
附图说明
图1为30μm铂铝涂层的表面形貌。
图2为30μm铂铝涂层的截面形貌。
图3为30μm铂铝涂层在1000℃预氧化后的表面形貌。
图4为30μm铂铝涂层在1000℃预氧化后的截面形貌。
图5为1000℃预氧化的TBCs试样(30μm铂铝涂层)在1100℃进行450h热循环后的截面形貌。
图6为1000℃预氧化的TBCs试样(30μm铂铝涂层)在1100℃下经过2200次热冲击后的截面形貌。
图7为30μm铂铝涂层在900℃预氧化后的表面形貌。
图8为900℃预氧化的TBCs试样(30μm铂铝涂层)在1100℃进行450h热循环后的截面形貌。
图9为900℃预氧化的TBCs试样(30μm铂铝涂层)在1100℃下经过2200次热冲击后的截面形貌。
图10为无预氧化、900℃预氧化以及1000℃预氧化的TBCs试样(30μm铂铝涂层)在1100℃恒温氧化净增重曲线。
图11为无预氧化、900℃预氧化以及1000℃预氧化的TBCs试样(30μm铂铝涂层)热冲击和热循环实验的试样表面状态。
具体实施方式
为了进一步理解本发明,以下结合实例对本发明进行描述,但实例仅为对本发明的特点和优点做进一步阐述,而不是对本发明权利要求的限制。
本发明提供一种用于提高基于铂铝粘结层的热障涂层寿命的方法,具体过程如下:
(1)在基体上制备铝铂涂层:
制备的铂铝涂层一般是先电镀铂再进行热处理,热处理温度一般为1000℃-1100℃,热处理时间一般为1-3小时;热处理后采用化学气相沉积的方法沉积铝,沉积过程中(渗铝)温度为900℃-1100℃,时间3-6小时。
(2)低压预氧化处理:
将带有铂铝涂层的试样在真空条件下加热到900℃-1080℃,在该温度下进行保温3-8小时,并通入氧气,在涂层表面生成致密的氧化膜;保温结束后在真空条件下炉冷到100℃以下取样。
氧化过程是采用管式炉在真空条件下加热和冷却,一般真空度为1.5×10-1Pa,在负压条件下发生氧化,生成致密的氧化铝薄膜。
(3)在TGO氧化膜表面沉积厚度为80~250μm的YSZ氧化钇改性氧化锆涂层。
实施例1:
基材采用定向凝固镍基高温合金DD5。
其化学成分如下(质量百分比):Co:7.5%,Cr:7%,W:5%,Mo:1.5%,Al:6.2%,Ta:6.5%,Re:3%,Ni:余量。将直径为13mm的DD5高温合金棒用线切割加工成厚2毫米的圆片,在圆片的上方正中间位置切Φ3mm的圆孔,以方便电镀和气相沉积的过程中悬挂。
利用电镀制备铂层,再采用CVD引入铝离子,制备的铂铝涂层为30μm,表面和截面形貌如图1和图2所示。该铂铝涂层外层1/3处Pt含量为10~40wt%,Ni含量为30-40wt%,Al含量为20-40wt%。
将制备好铂铝涂层的合金试样放入管式炉中,通入氩气对炉膛进行洗气;
洗气结束后,进行抽真空,当炉内达到压强为1.5×10-1Pa时,开始以10-15℃/min速度加热到1000℃;
到温后,通入流量为35ml/min的99.99%纯氧,并在1000℃保温5h进行氧化,此时炉内压强在25Pa左右;
氧化结束后,停止通入氧气,在真空条件下进行炉冷,当温度下降到100℃以下取样。
对样品进行检测发现涂层表面为致密的α-Al2O3,形貌如图3所示,氧化膜的厚度为1.2微米,如图4所示。
在预氧化后的铂铝粘结层上制备YSZ氧化钇改性氧化锆并进行了恒温氧化实验、热循环实验和热冲击实验。1100℃恒温氧化得到的试样净增重曲线如图10所示,相对于铂铝涂层,1000℃预氧化后的试样增重最小。1100℃热循环450小时后的实验截面如图5所示。1100℃的热冲击2200次的试样截面如图6所示。热循环和热冲击实验的试样情况如图11所示,根据图可知,添加预氧化工艺后涂层在经过长时间的热循环和热冲击时具有较好的结合力,。
实施例2:
基体采用DD5高温合金,将直径为13毫米的高温合金棒用线切割加工成厚2毫米的圆片,在圆片的上方正中间位置切Φ3mm的圆孔,以方便电镀和气相沉积的过程当中悬挂。
利用电镀和化学气相沉积的方法制备30μm铂铝涂层,表面和截面如图1和图2所示;
在管式炉中利用氩气对炉膛进行洗气处理,洗气结束后,进行抽真空,当炉内达到压强为1.5×10-1Pa时,开始以10-15℃/min速度加热到900℃;
到温后,通入流量为35ml/min的99.99%纯氧,并在900℃保温5h进行氧化,此时炉内压强在15Pa左右;
氧化结束后停止通入氧气,在真空条件下进行炉冷,当温度下降到100℃以下取样。预氧化后的表面形貌图如图7所示,涂层表面形成了致密的氧化铝薄膜。
在预氧化后的铂铝粘结层上制备YSZ氧化钇改性氧化锆并进行了恒温氧化实验、热循环实验和热冲击实验。1100℃恒温氧化得到的试样净增重曲线如图10所示,相对于铂铝涂层,具有较小的增重。1100℃热循环450小时后的试样截面如图8所示。1100℃热冲击2200次的试样截面如图9所示。热循环和热冲击试样表面状况如图11所示,根据图可知,添加预氧化工艺后涂层在经过长时间的热循环和热冲击时具有较好的结合力。
Claims (9)
1.一种用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:该方法首先在基体表面制备铂铝涂层,然后采用低压预氧化工艺在铂铝涂层表面形成一层致密TGO获得铂铝粘结层,最后在所述TGO上面制备YSZ氧化钇改性氧化锆涂层。
2.根据权利要求1所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述基体为CMSX-4、DD419、Rene5或DD5合金。
3.根据权利要求1所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述铂铝涂层化学成分为:Pt为10-40wt%,Al为20-40wt%,Ni为30-40wt%;所述涂层中β-(Ni,Pt)Al为主相。
4.根据权利要求1所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述铂铝涂层厚度为20~60μm。
5.根据权利要求1所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述低压预氧化工艺是指采用氧气对基体上的铂铝涂层进行处理,其中:处理压力为1×10-2~1×103Pa,处理温度为900~1080℃,处理时间为3~8h,通入浓度≥99.99%纯氧,通入纯氧流量为1~300ml/min。
6.根据权利要求5所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述低压预氧化工艺中,在真空条件下加热,达到处理温度900℃-1080℃后通入氧气,保温结束后停止通入气体,在真空条件下炉冷到100℃以下取样。
7.根据权利要求5所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述铂铝涂层采用低压预氧化工艺处理后,铂铝涂层表面生成一层TGO氧化膜,TGO氧化膜厚度为0.5~4μm。
8.根据权利要求5或7所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述TGO氧化膜为α-Al2O3,生成TGO氧化膜的表面粗糙度为Ra 0.5~1.6。
9.根据权利要求1所述的用于提高基于铂铝粘结层的热障涂层寿命的方法,其特征在于:所述YSZ氧化钇改性氧化锆涂层的厚度为80~250μm。
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