CN101802243B - 隔热涂层材料 - Google Patents
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Abstract
本发明提供导热率低于稀土稳定氧化锆的隔热涂层材料。一种隔热涂层材料,含有组成式(1):Ln1-xTaxO1.5+x(其中,0.13≤x≤0.24,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的化合物作为主体。以及,一种隔热涂层材料,含有组成式(2):Ln1-xNbxO1.5+x(其中,0.13≤x≤0.24,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的化合物作为主体。以及,一种隔热涂层材料,含有组成式(3):Ln3NbO7(其中,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的、具有萤石结构的立方晶系化合物作为主体。
Description
技术领域
本发明涉及能够应用于发电用燃气轮机的动叶片、静叶片和燃烧室、以及喷气发动机等在高温环境下使用的设备部件的隔热涂层材料。
背景技术
为了燃气轮机和喷气发动机等的高效率化,其燃气的高温化不断升级。为了保护金属制部件免受高温(例如,在1700℃级的燃气轮机内,叶片最高表面温度约为1350℃)的影响,在部件的表面涂布有隔热涂层(Thermal Barrier Coating,TBC)。作为该隔热涂层的材料,使用以氧化钇稳定氧化锆(YSZ)等稀土稳定氧化锆为代表的低导热性陶瓷。在作为金属制部件的基材上通过真空等离子体射流等涂布金属接合层后,在金属接合层上通过大气压等离子体射流涂布隔热涂层。
利用大气压等离子体射流在金属制部件上涂布的隔热涂层,不具有致密的组织,在内部具有许多气孔。图1是隔热涂层的组织的示意图。如该图所示,隔热材料1的组织中,存在直径达数十μm的大气孔2、直径为数μm程度的小气孔3、宽度较窄的线状气孔4、5等各种形状的气孔。隔热材料1本身为低导热性的陶瓷,同时利用内部存在的这样的许多气孔2~5来保持材料的隔热性能,从而使作为基材的金属制部件能够在高温环境下使用。
稀土稳定氧化锆,在作为可忽视气孔的致密的烧结体进行评价时导热率为2.2W/mK,即使在陶瓷材料中也较低,另外,线膨胀系数大,并且韧性高。因此,稀土稳定氧化锆适用于隔热涂层材料。
近年来,对于提高隔热性的需求不断增长,而在将稀土稳定氧化锆用于隔热涂层材料时,为了进一步提高隔热性,需要加厚涂膜。但是,由于膜变厚而存在容易发生膜的破裂或剥离的问题。因此,为了实现不改变膜厚也具有高隔热性的隔热涂层,期待开发具有更低导热性的材料,例如开发导热率约为目前的1/2的材料。
作为具有低导热性的材料,例如专利文献1中,公开了在稀土稳定氧化锆及稀土稳定氧化锆-氧化铪中添加0.1~10摩尔%氧化镧的、低导热率的隔热涂层材料。
专利文献2中,作为具有低导热率的隔热涂层材料,公开了含有Ln3Nb1-xTaxO7(其中,0≤x≤1,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的化合物作为主体的材料。
专利文献1:日本特开2004-270032号公报
专利文献2:日本特开2006-298695号公报
发明内容
专利文献2的隔热涂层材料,从室温到高温不发生相转变,在使用温度范围内的相稳定性良好。另外,具有与稀土稳定氧化锆同等或高于稀土稳定氧化锆的熔点,并且显示低于稀土稳定氧化锆的导热性。因此,有望作为隔热涂层材料使用。但是,为了实现更高的隔热性,需要显示更低导热性的隔热涂层材料。
本发明是为了解决上述课题而完成的,其目的在于提供导热率低于稀土稳定氧化锆的隔热涂层材料。
为了解决上述课题,本发明人进行了反复研究,结果发现:由Ln1-xTaxO1.5+x或Ln1-xNbxO1.5+x(Ln为选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的、满足0.13≤x≤0.24的化合物,显示出与稀土稳定氧化锆同等程度的线膨胀系数,并且具有低导热性。并且发现:在Ln的平均离子半径r为的情况下,能够得到从高温到低温(室温)不发生相转变、在机械强度方面具有稳定性的隔热涂层。
即,本发明提供一种隔热涂层材料,其中,含有组成式(1):
Ln1-xTaxO1.5+x
(式中,0.13≤x≤0.24,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)
表示的化合物作为主体。
另外,本发明提供一种隔热涂层材料,其中,含有组成式(2):
Ln1-xNbxO1.5+x
(式中,0.13≤x≤0.24,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)
表示的化合物作为主体。
组成式(1)或组成式(2)表示的化合物,由于氧缺陷不规则导致声子的散射增加,因此具有低于现有的稀土稳定氧化锆的导热率。因此,不需要象现有的稀土稳定氧化锆那样通过加厚膜来提高隔热性,即使是与目前同等程度的膜厚,也能够得到隔热性高于稀土稳定氧化锆的隔热涂层。
如果设定x≤0.24,则与现有的Ln3TaO7及Ln3NbO7(x=0.25)相比导入更多的氧缺陷,因此声子的散射效果变得更高,导热性进一步降低。但是,如果x<0.13,则Ln2O3超出固溶极限而析出,因而导热率增大。因此,x的值设定为0.13≤x≤0.24,优选0.15≤x≤0.23,更优选0.18≤x≤0.22。
上述发明中,优选所述Ln的平均离子半径小于在Ln的平均离子半径小于的情况下,组成式(1)或组成式(2)的化合物从高温到低温(室温)不发生相转变。因此,即使在例如燃气轮机发动或停止时等遭受急剧的温度变化的情况下,也不会发生随相转变而产生的急剧的体积变化,从而能够防止隔热涂层的破裂或剥离。另外,本发明中的离子半径的值,根据R.D.Shannon,Acta Crystallogr.,A32,751(1976)而确定。
另外,本发明的隔热涂层材料是指作为原材料的隔热涂层材料,并且也包括在设备部件的表面形成的隔热涂层。
具有上述隔热涂层材料的设备部件,具备隔热性高、即使在遭受急剧的温度变化的情况下也不易发生破裂或剥离的隔热涂层,因此成为能够耐受高温下使用的设备部件。作为设备部件,可以列举:发电用燃气轮机的动叶片、静叶片和燃烧室、以及喷气发动机等。
另外,为了解决上述课题,本发明人进行了反复研究,结果发现:在Ln3NbO7(Ln为选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)表示的化合物中,特别是具有萤石结构的立方晶系化合物显示出与稀土稳定氧化锆同等程度的线膨胀系数,并且具有低导热性。并且发现:Ln3NbO7表示的化合物的晶体结构随着以摩尔分数算术平均的稀土类元素Ln的平均离子半径而改变,在Ln的平均离子半径r为 时,化合物Ln3NbO7成为萤石结构,具有更低的导热率。在此,本发明中离子半径的值,根据R.D.Shannon,Acta Crystallogr.,A32,751(1976)而确定。
即,本发明提供一种隔热涂层材料,其中,含有组成式(3):
Ln3NbO7
(式中,0.13≤x≤0.24,Ln表示选自由Sc、Y及镧系元素组成的组中的一种或两种以上元素)
表示的、具有萤石结构的立方晶系化合物作为主体。
这样,组成式(3)表示的具有萤石结构的立方晶系化合物,通过使氧缺陷不规则化而增加声子的散射,因此,得到低于现有稀土稳定氧化锆的导热率。
一般认为导热率的误差为±0.1W/mK,因此如果化合物Ln3NbO7的导热率为1.2W/mK以下,则能够实现具有现有稀土稳定氧化锆的1/2导热率的隔热涂层材料。因此,将其用于隔热涂层时,不需要象现有的稀土稳定氧化锆那样通过加厚膜来提高隔热性,即使是与目前同等程度的膜厚,也能够得到隔热性高于稀土稳定氧化锆的隔热涂层。
另外,本发明的隔热涂层材料,是指作为原材料的隔热涂层材料,并且也包括在设备部件的表面形成的隔热涂层。
根据本发明,通过使隔热涂层材料含有上述组成式(1)、组成式(2)或组成式(3)表示的化合物作为主体,能够得到低于现有稀土稳定氧化锆的导热率。由此,能够提供隔热性提高、并且不易发生破裂或剥离的隔热涂膜。如果将本发明的隔热涂层材料用于例如1700℃级的燃气轮机,则金属制部件在高温环境下的耐久性提高,因此能够实现燃气轮机的高效率化。
附图说明
图1是隔热涂层的组织的示意图;
图2是表示组成式Yb1-xTaxO1.5+x中的x值与导热率的关系的图表;
图3表示组成式Y1-xTaxO1.5+x中的x值与导热率的关系的图表;
图4是表示Ln的平均离子半径与导热率的关系的图表。
标记的说明
1隔热涂层材料
2直径数十μm的大气孔
3直径数μm的小气孔
4线状气孔
5线状气孔
具体实施方式
以下,说明本发明的隔热涂层材料的第一实施方式。
本发明的隔热涂层材料含有Ln1-xTaxO1.5+x或Ln1-xNbxO1.5+x表示的化合物作为主体。Ln表示选自Sc、Y及镧系元素(La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)中的一种或两种以上元素。
Ln1-xTaxO1.5+x或Ln1-xNbxO1.5+x显示低于现有稀土稳定氧化锆的导热率。认为其原因在于通过使结构中的氧缺陷不规则化而增加了声子的散射。特别是在x值为0.13≤x≤0.24的情况下,Ln与Ta或Nb固溶化,使氧缺陷进一步增加从而提高不规则性,因此得到导热率低的隔热涂层材料。优选设定0.15≤x≤0.23,更优选0.18≤x≤0.22时,能够进一步降低导热率。
Ln1-xTaxO1.5+x或Ln1-xNbxO1.5+x的晶体结构,在Ln的平均离子半径的情况下,从高温到低温不发生相转变。因此,即使在高温下运转的设备发动或停止时等温度急剧变化的情况下,也不会发生随相转变而产生的急剧的体积变化,因此能够防止隔热涂层的破裂或剥离。
作为满足的元素,可以列举:Lu、Yb、Tm、Er、Ho及Y。特别是Yb、Er和Y由于是克拉克值较大的元素,因此优选用作隔热涂层材料。作为组成式(1)或组成式(2)中的Ln,可以从Lu、Yb、Tm、Er、Ho及Y中选择一种,也可以选择两种以上。或者,可以从Lu、Yb、Tm、Er、Ho及Y中选择一种或两种以上元素,再从其它的 的元素中选择一种或两种以上元素。在这种情况下,为了使所选元素的平均离子半径满足需要适当设定组成比。
含有组成式(1)或组成式(2)表示的化合物的隔热涂层,可以通过大气压等离子体射流法或电子束蒸镀法等,借助金属接合层在金属制部件(设备部件)上形成。为提高隔热性而增加膜厚是有效的,但是容易发生隔热涂层的破裂或剥离,因此,隔热涂层的膜厚为约0.3mm~约0.5mm是适当的。由于组成式(1)或组成式(2)表示的化合物的导热率低,因此不加厚膜也能够得到可耐受在高温环境下使用的、具有高隔热性的隔热涂层。
以下,给出实施例1具体说明本发明。但是,本发明并不限定于此。
(实施例1)
使用Ta2O5、Yb2O3、Y2O3作为原料粉末,按照所需组成称量,并用球磨机进行固相混合。将混合粉末干燥后,在1400℃下煅烧。通过粉末X射线衍射鉴定煅烧粉末,结果确认:没有残留未反应原料成分,所有试样均成为单相。
将各试样在1600℃下焙烧,从其烧结体上切出直径10mmφ、厚度1mm的圆盘状试样,利用激光闪光法测定导热率。
图2表示组成式Yb1-xTaxO1.5+x的组成与导热率的关系。该图中,横轴为组成式Yb1-xTaxO1.5+x中的x值,纵轴为导热率。在x=0.2的附近导热率最小(约0.8W/mK)。在0.13≤x≤0.24时,导热率为1.1W/mK以下,为现有YSZ的导热率的1/2以下,并且低于Yb3TaO7(x=0.25)的导热率。特别是在0.15≤x≤0.23时,能够实现1.0W/mK以下的导热率,0.18≤x≤0.22时,能够实现0.9W/mK以下的导热率。
图3表示组成式Y1-xTaxO1.5+x的组成与导热率的关系。该图中,横轴为组成式Y1-xTaxO1.5+x中的x值,纵轴为导热率。与化合物Yb1-xTaxO1.5+x的情况相同,在x=0.2的附近导热率最小(约0.8W/mK),在0.13≤x≤0.24时,能够得到1.1W/mK以下的导热率。
表1表示化合物Y1-xTaxO1.5+x、化合物Y1-xTaxO1.5+x、及作为比较材料的YSZ(添加有8摩尔%Y2O3的ZrO2)的平均线膨胀系数。
表1
试样名称 | 平均线膨胀系数(1/K)RT~1000℃ |
ZrO2-8摩尔%Y2O3 | 1.02×10-5 |
Yb0.8Ta0.2O1.7 | 1.00×10-5 |
Y0.8Ta0.2O1.7 | 1.01×10-5 |
本发明的化合物显示与现有YSZ等同的线膨胀系数。
Nb是与Ta同族的元素,因此,Ln1-xNbxO1.5+x表示的化合物的情况下,也同样在0.13≤x≤0.24时导热率低,具有与现有YSZ等同的线膨胀系数。
以下,说明本发明的隔热涂层材料的第二实施方式。
本发明的隔热涂层材料含有组成式(3)表示的化合物作为主体。Ln表示选自Sc、Y及镧系元素(La、Ce、Pr、Nd、Pm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)中的一种或两种以上元素。
化合物Ln3NbO7的晶体结构对应于Ln的平均离子半径r而改变。在此,Ln的平均离子半径r是将构成Ln的各元素的离子半径用摩尔分数算术平均而得到的值。在Ln的平均离子半径r为以上的情况下,化合物Ln3NbO7的晶体结构成为斜方晶,而在Ln的平均离子半径r小于的情况下,成为具有萤石结构的立方晶。
具有萤石结构的立方晶系的Ln3NbO7,显示低于现有稀土稳定氧化锆的导热率。认为其原因在于通过使结构中的氧缺陷不规则化而增加了声子的散射。特别是Ln由两种以上元素构成时,不规则性进一步提高。由此使声子的散射进一步增加,因此能够有效地实现低导热率的隔热涂层材料。
特别是Ln的平均离子半径r为时,化合物Ln3NbO7显示低导热率而成为隔热性优良的涂层材料,因此优选。另外,如果Ln的平均离子半径r为则化合物Ln3NbO7的导热率为1.1W/mK以下,达到现有YSZ的导热率的1/2以下,因此更适合作为隔热涂层材料。
含有化合物Ln3NbO7的隔热涂层,可以通过大气压等离子体射流法或电子束蒸镀法等,借助金属接合层在金属制部件(设备部件)上形成。为提高隔热性而增加膜厚是有效的,但是容易发生隔热涂层的破裂或剥离,因此,隔热涂层的膜厚为约0.3mm~约0.5mm是适当的。如果本发明的化合物Ln3NbO7的导热率为1.2W/mK以下,则不加厚膜也能够得到可耐受在高温环境下使用的、具有高隔热性的隔热涂层。
以下,给出实施例2具体说明本发明。但是,本发明并不限定于此。
(实施例2)
适当选择与Ln相当的元素的种类和比率,使Ln的平均离子半径小于使用Nb2O5、Sc2O3、Y2O3及3价的镧系元素氧化物(La2O3、Ce2O3等)作为原料粉末,按照所需组成称量,并用球磨机进行固相混合。将混合粉末干燥后,在1400℃下煅烧。通过粉末X射线衍射鉴定该煅烧粉末,结果确认:没有残留未反应原料成分,所有试样均成为单相。
将这些试样在1600℃下焙烧,从其烧结体上切出直径10mmφ、厚度1mm的圆盘状试样,利用激光闪光法测定导热率。
(比较例)
表2表示实施例2及比较例制作的试样的Ln的平均离子半径、晶体结构及导热率。作为比较,表2中记载了氧化钇稳定氧化锆(YSZ)的导热率。
另外,图4表示Ln的平均离子半径与导热率的关系。
表2
如表2所示,Ln的平均离子半径小于的化合物具有萤石结构,显示1.3W/mK以下的低导热率。另一方面,Ln的平均离子半径为以上的化合物其晶体结构变为斜方晶,导热率为1.4W/mK以上,大于具有萤石结构的化合物的导热率。
表3表示实施例2的化合物(Nd0.5Yb2.5NbO7)和YSZ的平均线膨胀系数。实施例2的化合物显示与现有YSZ同等程度的线热膨胀系数。
表3
试样名称 | 平均线热膨胀系数(1/K)RT~1000℃ |
ZrO2-8摩尔%Y2O3 | 1.02×10-5 |
Nd0.5Yb2.5NbO7 | 1.04×10-5 |
如果将导热率为1.2W/mK以下的化合物Ln3NbO7用于隔热涂层,则得到具有高隔热性的隔热涂层,如果将其用于例如1700℃级的燃气轮机,则金属制部件在高温环境下的耐久性提高,因此能够实现燃气轮机的高效率化。
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