CN102187013B - 隔热涂层用材料、隔热涂层、涡轮部材及燃气轮机 - Google Patents

隔热涂层用材料、隔热涂层、涡轮部材及燃气轮机 Download PDF

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CN102187013B
CN102187013B CN2009801411802A CN200980141180A CN102187013B CN 102187013 B CN102187013 B CN 102187013B CN 2009801411802 A CN2009801411802 A CN 2009801411802A CN 200980141180 A CN200980141180 A CN 200980141180A CN 102187013 B CN102187013 B CN 102187013B
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heat insulating
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turbine
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鸟越泰治
永野一郎
冈田郁生
塚越敬三
高桥孝二
冈岛芳史
霞总司
伊藤荣作
森一刚
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Abstract

本发明的目的在于提供一种与YSZ相比高温结晶稳定性优异、具有高韧性且具有高隔热效果的隔热涂层用材料。另外，提供一种具有使用该隔热涂层用材料形成的陶瓷层的热循环耐久性优异的隔热涂层、以及具备该隔热涂层的涡轮用部材及燃气轮机。隔热涂层用材料以含有作为稳定剂的Yb2O3和Sm2O3的ZrO2为主，所述稳定剂的含量为2mol％以上7mol％以下，所述Sm2O3的含量为0.1mol％以上2.5mol％以下。

Description

隔热涂层用材料、隔热涂层、涡轮部材及燃气轮机
技术领域
本发明涉及一种耐久性优异的隔热涂层用材料，尤其是涉及作为隔热涂层的外涂层使用的陶瓷层。 
背景技术
近年来，作为节能对策之一，正在研究提高火力发电的热效率。为了使发电用燃气轮机的发电效率提高，升高气体入口温度是有效的，该温度有时也设为1500℃左右。为了实现这样的发电装置的高温化，需要将构成燃气轮机的静叶、动叶、或者燃烧器的壁材等用耐热部材构成。但涡轮叶的材料是耐热金属，即便如此也不能耐受这样的高温。因此，形成隔热涂层(Thermal Barrier Coating，TBC)保护耐热金属基材免受高温损害。隔热涂层通过金属结合层在耐热金属的基材上，利用喷镀等成膜方法层叠含有氧化物陶瓷的陶瓷层而形成。作为陶瓷层，使用ZrO2系的材料。尤其是用Y2O3部分稳定化或完全稳定化的ZrO2即YSZ(钇稳定化氧化锆)，在陶瓷材料中具有比较低的热传导率和比较高的热膨胀率，所以被广泛使用。 
然而，根据燃气轮机的种类，可以考虑使涡轮的入口温度升高到超过1500℃的温度。另外，由于近年来环境对策的关系，开发热效率更高的燃气轮机正在进行，可考虑涡轮的入口温度也达到1700℃，设想涡轮叶的表面温度也达到1300℃的高温。 
在通过具备含有上述YSZ的陶瓷层的隔热涂层材料包覆燃气轮机的动叶、静叶等时，在超过1500℃的严酷运转条件下，燃气轮机的运转中，有可能上述陶瓷层的一部分剥离，耐热性受损。另外，YSZ在超过1200℃的温度下产生脱稳定化现象，耐久性会大幅降低。 
作为在高温环境下的结晶稳定性优异、具有高热耐久性的隔热涂层，例如，开发了添加Yb2O3的ZrO2(专利文献1)、添加Dy2O3的ZrO2(专 利文献2)、添加Er2O3的ZrO2(专利文献3)、SmYbZr2O7(专利文献4)。 
专利文献 
专利文献1：日本特开2003-160852号公报(权利要求1、段落[0006]、[0027]～[0030]) 
专利文献2：日本特开2001-348655号公报(权利要求4及5、段落[0010]、[0011]、[0015]) 
专利文献3：日本特开2003-129210号公报(权利要求1、段落[0013]、[0015]) 
专利文献4：日本特开2007-270245号公报(权利要求2、段落[0028]、[0029]) 
发明内容
对于涡轮叶的隔热涂层，进一步要求高的热循环耐久性、高温结晶稳定性及高隔热性。但是，兼顾这些是非常困难的。 
本发明的目的在于，提供一种与YSZ相比高温结晶稳定性更优异、具有高韧性且具有高隔热效果的隔热涂层用材料。另外，其目的还在于，提供一种具有使用该隔热涂层用材料形成的陶瓷层的热循环耐久性优异的隔热涂层、以及具备该隔热涂层的涡轮用部材及燃气轮机。 
即，本发明的第1方案为一种隔热涂层用材料，其以含有作为稳定剂的Yb2O3和Sm2O3的ZrO2为主，前述稳定剂的含量为2mol％以上7mol％以下，前述Sm2O3的含量为0.1mol％以上2.5mol％以下。 
前述Sm2O3的含量更优选1.0mol％以上2.0mol％以下。 
由于Yb(镱)与Y(钇)相比粒子半径小，所以在高温下具备优异的结晶稳定性。含有Yb2O3作为稳定剂的ZrO2，与YSZ相比难以引起伴随温度变化的相变，也可以抑制相变引起的应力的发生。 
通过Zr(锆)含有原子量不同的Yb和Sm(钐)，从而晶格失配被导入而使晶体结构复杂。由此容易产生热散射，实现降低热传导率的效果。 
隔热涂层用材料中的稳定剂的含量(Yb2O3和Sm2O3总计)不足2mol％时，容易发生向单斜晶相的相变，因此稳定剂的含量优选2mol％以上。另一方面，稳定剂的含量多于7mol％时，往往准稳定的正方晶相减少。 因此，破坏韧性降低，所以稳定剂的含量优选7mol％以下。 
Sm2O3的含量少于0.1mol％时，无法得到所期望的热传导率，所以Sm2O3的含量优选0.1mol％以上。另一方面，Sm2O3的含量多于2.5mol％时，虽然热传导率降低，但无法得到高的破坏韧性值。因此，Sm2O3的含量优选2.5mol％以下 
第1方案所述的隔热涂层用材料，由于以上述范围的量含有Yb2O3和Sm2O3作为稳定剂，所以不仅具有在高温下的结晶稳定性，而且可以兼顾高韧性和低热传导性。因此，可以制成热循环耐久性优异的隔热涂层。 
第2方案所述的隔热涂层，优选在耐热合金基材上具备金属结合层、和在该金属结合层上形成的含有上述的隔热涂层用材料的陶瓷层。 
含有上述隔热涂层用材料的陶瓷层，高温结晶稳定性优异，具有高韧性。因此，成为热循环耐久性优异的隔热涂层。 
本发明的另外的方案为一种具备上述隔热涂层的涡轮部材、及具备该涡轮部材的燃气轮机。 
根据所述构成的涡轮部材，可以制成具备优异的高温结晶稳定性和热循环耐久性的涡轮部材。由此，还可构成可靠性更优异的燃气轮机。 
上述组成的隔热涂层用材料，在高温下的结晶稳定性优异，具有高的破坏韧性和低的热传导率。由此，可以制成热循环耐久性优异、具备高隔热效果的隔热涂层。 
附图说明
图1是应用了本实施方式涉及的隔热涂层用材料的涡轮部材的剖面的示意图。 
图2是表示实施例中的烧结体中的Sm2O3含量和破坏韧性值的关系的图。 
图3是表示实施例中的烧结体中的Sm2O3含量和热传导率的关系的图。 
具体实施方式
以下对本发明的实施方式进行说明。 
图1是应用了本实施方式涉及的隔热涂层用材料的涡轮部材的部分剖面示意图。在涡轮动叶等的耐热合金基材11上按顺序形成金属结合层12和陶瓷层13作为隔热涂层。 
金属结合层12为MCrAlY合金(M表示Ni、Co、Fe等金属元素或它们中的2种以上的组合)等。 
本实施方式涉及的构成陶瓷层13的隔热涂层用材料，包含含有作为稳定剂的Yb2O3和Sm2O3的ZrO2。稳定剂的含量设为2mol％以上7mol％以下，且Sm2O3的含量设为0.1mol％以上2.5mol％以下。Sm2O3的含量更优选1.0mol％以上2.0mol％以下。 
本实施方式的隔热涂层用材料，作为稳定剂含有包含粒子半径比Y小且高温下的稳定性高的Yb的Yb2O3。由此，得到高的破坏韧性值，成为热循环耐久性优异的隔热涂层。 
本实施方式的隔热涂层用材料，通过含有与Zr相比原子量更大的Yb和Sm，晶格失配被导入而晶体结构变复杂。因此，容易产生热散射，实现热传导率降低这样的效果。其结果成为热传导率低的陶瓷层。 
上述陶瓷层13，为了在提高隔热性的同时，使杨氏模量降低且提高隔热涂层的热循环耐久性，通常导入10％左右的气孔。 
上述陶瓷层13通过大气压等离子体喷镀、电子束物理蒸镀等成膜。应用大气压等离子体喷镀时，本实施方式的隔热涂层用材料利用喷雾干燥法等进行喷镀粉末。 
以下通过实施例对本实施方式的隔热涂层用材料及隔热涂层进行详细说明。 
(实施例1) 
将表1示出的各组成的烧结体用常压烧结法在烧结温度1600℃、烧结时间5小时的条件下制作。原料粉末使用Yb2O3、Sm2O3、ZrO2。 
[0039] 各组成的烧结体的破坏韧性值基于JIS R 1607进行测定。热传导率基于JIS R 1611规定的激光闪光法进行测定。对1300℃、1000小时加热处理前后的烧结体的构造相用粉末X射线衍射进行鉴定。 
(比较例1) 
使用添加了Y2O3：8mol％的ZrO2，在与实施例1同样的条件下制作烧结体。 
与实施例1同样，测定烧结体的破坏韧性、及热传导率。另外，与实施例1一样对加热处理前后的构造相进行测定。 
表1示出实施例1和比较例1的组成、各自的烧结体的特性。 
成膜后的构造相均是准稳定正方晶相。试料编号1～4(Yb2O3：4.45～2.3mol％、Sm2O3：0.05～2.2mol％)的烧结体在加热处理后的构造相中未确认到变化。另一方面，比较例和试料编号5及6(Yb2O3：0.1及0.05mol％、Sm2O3：4.4及4.45mol％)的烧结体通过加热处理产生相变，构造相为立方晶相+单斜晶相。 
[表1] 
图2表示烧结体中的Sm2O3含量和破坏韧性值的关系。在该图中，横轴为Sm2O3含量，纵轴为破坏韧性值。 
试料编号1～4的烧结体得到比比较例1(破坏韧性值：4MPa·m0.5)高的破坏韧性值。另一方面，试料编号5及6中，示出了比比较例1破坏韧性低的值。 
试料编号1中，由于多量添加了含有离子半径比Y小且高温下的结晶稳定性高的Yb的Yb2O3，所以得到高于比较例1的破坏韧性值。另一方面，依赖于Sm2O3的添加量增加，破坏韧性值降低。可以认为其原因在于Sm的离子半径比Y大。 
从该结果可以明确，Yb2O3的含量为2.3mol％以上，且Sm2O3的含量在0.05mol％～2.2mol％的范围内，可以得到高于比较例1的破坏韧性值，以Yb2O3为4.45mol％、且Sm2O3为0.05mol％的比例添加时显示出最高的破坏韧性值。 
图3表示烧结体中的Sm2O3含量和热传导率的关系。在该图中，横轴为Sm2O3含量、纵轴为热传导率。 
试料编号1～6的烧结体的热传导率低于比较例1的烧结体的热传导率，依赖于Sm2O3的含量而减少。可示出通过含有Yb2O3及Sm2O3，得到比比较例的热传导率低的热传导率。 
(实施例2) 
使用喷雾干燥法，制造粒径10～125μm的表1所示的各组合物的喷镀粉末。使用上述喷镀粉末，通过以下的方法制作形成有隔热涂层的试验片。 
在厚度5mm的合金金属基材(厂商：INCO公司、商标名：IN-738LC、化学组成：Ni-16Cr-8.5Co-1.75Mo-2.6W-1.75Ta-0.9Nb-3.4Ti-3.4Al(质量％))上，用低压等离子体喷镀法形成了膜厚100μm的金属结合层。金属结合层的组成为，Ni：32质量％、Cr：21质量％、Al：8％质量％、Y：0.5质量％、Co：剩余部分。 
利用大气压等离子体喷镀在金属结合层上喷镀上述喷镀粉末而制膜，形成膜厚0.5mm的喷镀被膜(陶瓷层13)。喷镀使用Sulzer Metco公司制的喷镀枪(F4枪)。喷镀条件为，喷镀电流：600(A)、喷镀距离：150(mm)、粉末供给量：60(g/min)、Ar/H2O：35/7.4(l/min)。喷镀被膜的气孔率为10％。气孔率使用光学显微镜(倍率100倍)对精密研磨而成的隔热涂层剖面拍摄任意5个视野(观察长度约4mm)，从由此得到的显微镜照片使用图像处理法算出被膜中气孔所占的比例。 
用上述工序制作的试验片，通过与实施例1同样的方法，测定喷镀被膜的热传导率。1300℃、1000小时的加热处理前后的构造相，通过与实施例1同样的方法进行鉴定，喷镀被膜气孔率用上述方法加以测定。 
利用激光热循环试验对试验片的热循环耐久性进行测定。关于试验条件，隔热涂层的最高表面加热温度：1400℃、最高界面温度：950℃、加热时间：3分钟、冷却时间：3分钟，测量到陶瓷层剥离前的热循环数。 
(比较例2) 
另外，与实施例2同样，喷镀表1的组成的隔热涂层用材料使其成膜，制作了试验片。 
与实施例1同样操作，测定了喷镀被膜的热传导率、加热处理前后的气孔率及构造相，与实施例2同样操作，测定了试验片的热循环耐久性。 
喷镀被膜的热传导率及加热处理前后的构造相，显示与实施例1和比较例1的烧结体同样的倾向。 
表2示出喷镀被膜的特性。 
[表2] 
Figure DEST_PATH_GPA00001348605500031
试料编号1～4中，加热处理前后的喷镀被膜的构造相均是准稳定性正方晶相。因此，就试料编号1～4的试验片而言，可以为300次以上的热循环。另一方面，比较例与试料编号5及6通过加热处理，构造相从准稳定性正方晶相变化到立方晶相和单斜晶相的混合晶相。综上，就试料编号1～4的烧结体的试验片而言，可得到高于比较例的试验片的热循环耐久性。 
就试料编号2～6而言，加热处理后的喷镀被膜的气孔率比加热前降低0.2％。另一方面，就比较例和试料编号1而言，加热处理后的喷镀被膜的气孔率降低1％和3％。 
图中 
11 耐热合金基材 
12 金属结合层 
13 陶瓷层 

Claims (4)

1.一种隔热涂层用材料，以含有稳定剂的ZrO2为主，所述稳定剂为Yb2O3和Sm2O3，
所述稳定剂的含量为2mol％以上7mol％以下，
所述Sm2O3的含量为0.1mol％以上2.5mol％以下。
2.一种隔热涂层，其在耐热合金基材上具备金属结合层、和在该金属结合层上形成的含有权利要求1所述的隔热涂层用材料的陶瓷层。
3.一种涡轮部材，其具备权利要求2所述的隔热涂层
4.一种燃气轮机，其具备权利要求3所述的涡轮部材。
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US11479846B2 (en) 2014-01-07 2022-10-25 Honeywell International Inc. Thermal barrier coatings for turbine engine components
JP6793039B2 (ja) * 2014-04-09 2020-12-02 ヌオーヴォ ピニォーネ ソチエタ レスポンサビリタ リミタータＮｕｏｖｏ Ｐｉｇｎｏｎｅ Ｓ．Ｒ．Ｌ． ターボ機関の構成部品を液滴侵食から保護する方法、構成部品及びターボ機関
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4533718B2 (ja) * 2000-06-16 2010-09-01 三菱重工業株式会社 遮熱コーティング材、遮熱コーティング材を適用したガスタービン部材およびガスタービン
CA2529781C (en) * 2004-12-14 2010-10-12 Mitsubishi Heavy Industries, Ltd. Thermal barrier coating material, thermal barrier member, and member coated with thermal barrier and method for manufacturing the same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3872632B2 (ja) 2000-06-09 2007-01-24 三菱重工業株式会社 遮熱コーティング材、それを適用したガスタービン部材およびガスタービン
US6812176B1 (en) * 2001-01-22 2004-11-02 Ohio Aerospace Institute Low conductivity and sintering-resistant thermal barrier coatings
JP4031631B2 (ja) 2001-10-24 2008-01-09 三菱重工業株式会社 遮熱コーティング材及びガスタービン部材並びにガスタービン
JP2003160852A (ja) 2001-11-26 2003-06-06 Mitsubishi Heavy Ind Ltd 遮熱コーティング材、その製造方法、タービン部材及びガスタービン
FR2838752B1 (fr) * 2002-04-22 2005-02-25 Snecma Moteurs Procede de formation d'un revetement ceramique sur un substrat par depot physique en phase vapeur sous faisceau d'electrons
WO2005017226A1 (en) * 2003-01-10 2005-02-24 University Of Connecticut Coatings, materials, articles, and methods of making thereof
US6960395B2 (en) * 2003-12-30 2005-11-01 General Electric Company Ceramic compositions useful for thermal barrier coatings having reduced thermal conductivity
US7255940B2 (en) * 2004-07-26 2007-08-14 General Electric Company Thermal barrier coatings with high fracture toughness underlayer for improved impact resistance
US7166373B2 (en) * 2004-08-19 2007-01-23 General Electric Company Ceramic compositions for thermal barrier coatings with improved mechanical properties
JP4969094B2 (ja) * 2004-12-14 2012-07-04 三菱重工業株式会社 遮熱コーティング部材及びその製造並びにガスタービン
US20070292624A1 (en) * 2005-06-28 2007-12-20 General Electric Company Low conductivity, thermal barrier coating system for ceramic matrix composite (CMC) articles
JP4959213B2 (ja) * 2006-03-31 2012-06-20 三菱重工業株式会社 遮熱コーティング部材及びその製造方法ならびに遮熱コート材料、ガスタービン及び焼結体
US7507484B2 (en) * 2006-12-01 2009-03-24 Siemens Energy, Inc. Bond coat compositions and arrangements of same capable of self healing
US20090184280A1 (en) * 2008-01-18 2009-07-23 Rolls-Royce Corp. Low Thermal Conductivity, CMAS-Resistant Thermal Barrier Coatings
US8047771B2 (en) * 2008-11-17 2011-11-01 Honeywell International Inc. Turbine nozzles and methods of manufacturing the same
US8470460B2 (en) * 2008-11-25 2013-06-25 Rolls-Royce Corporation Multilayer thermal barrier coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4533718B2 (ja) * 2000-06-16 2010-09-01 三菱重工業株式会社 遮熱コーティング材、遮熱コーティング材を適用したガスタービン部材およびガスタービン
CA2529781C (en) * 2004-12-14 2010-10-12 Mitsubishi Heavy Industries, Ltd. Thermal barrier coating material, thermal barrier member, and member coated with thermal barrier and method for manufacturing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP特开2007-270245A 2007.10.18
JP特许第4533718号B2 2010.09.01

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Patentee after: Mitsubishi Hitachi Power System Ltd.

Address before: Tokyo, Japan

Patentee before: Mit-subishi Heavy Industries Ltd.

CP01 Change in the name or title of a patent holder
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Address after: yokohama

Patentee after: Mitsubishi Power Co., Ltd

Address before: yokohama

Patentee before: MITSUBISHI HITACHI POWER SYSTEMS, Ltd.