CN1701951A - 具有可控孔隙率用于热障涂层的双层高速氧燃料涂层 - Google Patents
具有可控孔隙率用于热障涂层的双层高速氧燃料涂层 Download PDFInfo
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Abstract
在暴露于不友好热和化学环境的金属合金部件上使用的双层粘合层,金属合金部件如用于发电的燃气轮机发动机,和涂覆这种涂层的方法。优选的涂层包括涂到金属基底上的双层粘合层,两个层都使用高速氧燃料(HVOF)热喷涂来涂覆。在一种实施方案中,根据本发明的粘合层可与热障涂层(“TBC”)联合使用。但是,本发明还采取其它形式,如独立的覆层。根据本发明的双层粘合层由致密的第一内层(如铁、镍或钴-基合金)和第二外层组成,第一内层提供对金属基底的氧化保护,第二外层具有可控孔隙率,往往能提高粗糙度、机械顺从性和与TBC的粘着。优选地,双层粘合层的外部不太致密层由金属粉末和聚酯的混合物形成,以调整和控制孔隙率,但不损害机械顺从性。同时,这些层增强了与基底的粘着并提高了涂层体系的整体寿命。
Description
技术领域
本发明涉及金属合金部件的防护涂层,金属合金部件如暴露于高温气体环境和恶劣操作条件的燃气轮机发动机工作部件。更具体地,本发明涉及新型防护粘合层,该粘合层包括利用高速氧燃料(“HVOF”)热喷涂涂到金属基底的双层粘合层。在一种实施方案中,根据本发明的粘合层可与热障涂层(“TBC”)联合使用。但是,本发明也可采取其它形式,如独立的覆层。
根据本发明的典型双层粘合层包括提供防止金属基底氧化的第一致密内层,和具有可控孔隙率并往往改善粗糙度和有助于TBC与粘合层粘着的第二外层。优选地,双层粘合层的第二不太致密层由金属粉末和聚酯的混合物形成以控制和调整孔隙率到所需的水平。同时,这些层增强了粘合层和TBC之间的粘着并因此提高了涂层体系的整个寿命。
本发明还涉及形成双层粘合层的新方法,其中两个涂层都利用HVOF热喷涂涂到金属合金部件上。如下面所述,过去已将HVOF用于包含聚酯的涂层以控制涂层孔隙率,尤其是作为部分涂于金属基底的多层粘合层。
本发明尤其很好地适用于燃气轮机发动机部件,因为已知这类部件的操作条件在热力学和化学上是恶劣的。必然地,用于形成汽轮机、燃烧器和推力增强装置部件的金属基底的表面必须展现出大于在不友好高温气体环境中的平均机械强度、耐久性、耐氧化性和耐腐蚀性。
背景技术
近年来,通过在涂于汽轮机部件尤其是叶片和喷嘴金属基底的底涂层中掺入铁、镍和钴基成分的高温合金已在燃气轮机系统中取得了显著进展。例如,一些已有的涂层体系包括含有绝热陶瓷的顶层(一般称为热障涂层或“TBC”),和粘着到合金金属基底上的耐环境底部粘合层。已使用金属氧化物如部分或全部用氧化钇(Y2O3)稳定的氧化锆(ZrO2)、氧化镁(MgO)或其它氧化物,利用空气等离子喷涂(“APS”)、真空等离子喷涂(“VPS”)或物理气相沉积技术如电子束物理气相沉积(“EBPVD”)来形成绝热陶瓷层。参见普通转让的美国专利5981088(公开了使用通过EBPVD沉积的氧化钇稳定的氧化锆以提高热循环疲劳性能)。还可参见美国专利5817372(描述了沉积用于热障涂层体系的粘合层的方法);6165628(公开了金属基基底的防护涂层和相关方法);6274201(描述了金属基基底的防护涂层和相关方法);和6368672(公开了形成汽轮机发动机部件的热障涂层体系的方法)。
金属基底上的有效粘合层的目的有两方面。首先,涂层必须形成能保证下面的基材抗氧化、腐蚀和退化的致密防护粘着层。其次,涂层应足以促进陶瓷层的粘着。对于热喷涂涂层,需要高程度的表面粗糙度以提供机械联锁;EB-PVD TBCs需要平滑得多的界面粗糙度以允许TBC柱的更均匀生长。粘合层一般由合金制成,如MCrAlY,其中M代表金属如Ni、Co或Fe。铝化物粘合层经常用于EB-PVD TBC。由于粘合层成分已变得更复杂,因此同时得到较高的所需强度水平(尤其是在最大燃气轮机操作温度下)和令人满意的抗腐蚀和抗氧化水平已日益变得困难。近年来向着更高燃气轮机点火温度的趋势已使得氧化、腐蚀和退化问题甚至更加困难。
一般,已有体系中使用的粘合层基于抗氧化合金如McrAlY或能形成抗氧化金属间化合物的扩散铝化物或铝化铂。由这类成分形成的致密涂层通过在粘合层的最外表面处形成基底的防氧化层保护下面的合金。这种防氧化层一般为在高温下形成的致密粘着氧化铝层(有时称为“氧化铝皮”)。氧化皮往往保护粘合层免于连续氧化。如果粘合体具有相对粗糙的表面,则例如等离子喷涂的陶瓷层会很好地粘着到粘合层上。粘合层的粗糙表面通过粘合层和TBC微结构的联锁增强了机械粘着力。
对绝热陶瓷层和金属基底粘合层之间这种已知关系的描述出现在Zheng的普通自有的美国专利5817372中,本文引入其内容作为参考。‘372专利指出绝热陶瓷层和粘合层之间粘合体的强度和完整性通常取决于所涉及的沉积技术。也就是说,粘合层的结构和物理性能与沉积它们的方法和设备有关。
过去,通过热喷涂例如APS、VPS和HVOF技术涂粘合层,所有这些技术都需要使用金属粉末沉积粘合层。尽管利用这类技术沉积的粘合层已得到成功应用,但各自具有明显的优点和缺点,取决于所需的应用。例如,对于VPS,在沉积过程中发生非常少的金属颗粒氧化,因此得到的粘合层往往是致密的,相对地不含氧化物,并由于生长连续防护氧化皮的内在能力而表现出高温性能。VPS方法具有相对低的熔化喷涂粉末热容,因此一般使用粒度分布非常细的粉末。结果,VPS粘合层往往是致密的,但具有相对光滑的表面(一般200-350微英寸,即约4-约9μm))。因此,许多等离子喷涂的陶瓷层不能很好地粘着到下面的VPS粘合层上。专利5817372描述了通过使用在沉积过程中不完全熔化的粗粉末来产生粗糙度提高的VPS涂层。
空气等离子喷涂(APS)具有能熔化相对大颗粒的高热容,并允许使用能产生表面在一定程度上比通过VPS形成的表面粗糙的粘合层的金属粉末。因此,利用粗糙的APS粘合层表面正常地增强了陶瓷层与APS粘合层的粘着。这种粉末的粒度分布也宽,从而使得较细的颗粒可部分地填充较大颗粒之间的间隙并降低孔隙率。但是,APS中使用的较细颗粒易于在喷涂过程中氧化,一般产生氧化物含量非常高的粘合层。夹杂的氧化物和APS层中利用的较大粒度往往提高了涂层中的孔隙率。因此,APS粘合层内在地包含相对高含量的氧化物,并不如VPS粘合层致密,这使它们比VPS涂层更易于氧化。
用于涂粘合层的现有技术方法归结为三种通用的类:(1)通过APS、VPS或HVOF方法产生的完全致密涂层;(2)通过APS方法形成的完全多孔涂层;或(3)致密涂层后继以一个或多个多孔层的双层。双层涂层时常通过两种不同的方法产生(对于致密层,一般为HVOF或VPS,对于多孔层,一般为APS)。此双层结构也可通过改变粒度和/或喷涂参数以产生较粗糙或更加多孔的外层来形成。如上所述,迄今还没有使用HVOF来形成致密层和多孔层两个层。
使用两种不同的热喷涂方法来形成双层粘合层在制造过程中造成不希望有的复杂性。一般地,已知的HVOF/APS双层涂层在涂覆HVOF层后需要中间真空热处理。上面指出的‘732专利描述了一种这类双层粘合层体系,由使用不同粉末尺寸的两个HVOF层组成,以在表面提供增加的粗糙度。但是,外层接近于最大密度,并缺乏较多孔涂层的机械优点。现在认识到,使用单一的HVOF系统来涂双层涂层的致密层和多孔层两个层能大大简化制造工艺,并由于循环时间减少而导致成本降低。还可通过去掉‘372专利中描述的HVOF的中间真空热处理而获得循环时间的减少。
尽管一些现有技术的空气等离子喷涂涂层使用聚酯粉末作为挥发性填充剂,以调整和控制孔隙率(例如产生可研磨表面涂层),但使用聚酯填充剂在双层HVOF粘合层中产生孔隙率是未知的。已知通过HVOF技术沉积的粘合层对粉末的粒度分布非常敏感,因为HVOF的喷涂温度较低。因此,通常必须为粒度分布范围非常窄的粉末调整热喷涂参数。另外,为了使用HVOF方法产生有效的粘合层,必须使用粗粉末以便获得充分的表面粗糙度。但是,由于粗颗粒一般不能在较低的HVOF温度参数下全部熔化,因此由粗粉末形成的HVOF粘合层一般表现出较高的孔隙率和颗粒间较差的粘合。由细粉末形成的HVOF涂层较致密,但缺乏良好TBC粘着需要的足够粗糙度。
因此,尽管最近在粘合层方面有进展,包括与TBC联合使用的一些双层涂层,但本领域中仍存在对在暴露于燃气轮机发动机部件高温环境中的金属合金部件上的改进防护涂层的需要。也存在对涂覆这种涂层到暴露于高温不友好条件的关键汽轮机部件上的改进方法的需要。
发明内容
本发明提供一种新的粘合层,用于在不友好环境中使用的金属合金部件上的热障涂层,金属合金部件如燃气轮机发动机热气通道中存在的喷嘴、叶片、套管、机翼和其它部件。因此根据本发明的粘合层可被涂于燃气轮机“热段”中的部件上,包括燃烧器。在其它环境中可使用相同的方法,如在航空发动机中的推力增强装置部件中。因此,该涂层不限制于在工业燃气轮机上使用,而是也可应用于柴油机和其它内燃机中的选定部件。尽管本发明通常形成用于热障涂层(“TBC”)的粘合层,但也可用于形成独立的金属覆层,即没有任何陶瓷顶层。
如上所述,根据本发明的改进粘合层优选通过使用完全利用HVOF热喷涂涂覆的双层粘合层来形成。此双层涂层由致密内层和外层组成,内层提供对金属基底的氧化保护,外层具有可控孔隙率,往往提高粗糙度并提供改进的粘合层延展性,而不损害机械顺从性、强度或稳定性。令人惊奇的是,已发现可通过借助HVOF喷涂金属粉末和聚酯的混合物而形成具有可控孔隙率的第二HVOF外层。
本发明因此获得用于TBC体系的粘合层的三个理想属性,即防止氧气进入到基底的高密度材料层,促进与例如TBC粘着的高程度粗糙度,和为了良好机械顺从性的可控孔隙率。本领域中既使用HVOF又使用APS形成具有这些属性的双层粘合层的当前状况会被认为不是“制造友好”的,因为需要在制造过程中切换工艺方法,并在涂覆HVOF层后需要中间热处理。因此,通过单一的热喷涂方法制造致密内层和多孔外层并在用HVOF涂覆两个层后进行热处理,大大简化了制造工艺,降低了成本和提高了最终产品的机械性能。
还发现根据本发明的粘合层体系表现出提高的耐氧化性和因此延长的燃气轮机发动机循环寿命。根据本发明的典型HVOF双层涂层可在完成两个HVOF层后加以热处理,从而简化了制造工艺和降低了成本。因此,本发明提供仅仅通过HVOF加工而产生的有效双层粘合层,这比已有的HVOF/APS系统更容易和更节省成本。
从下面的详细描述中将能更好地理解本发明的其它目的和优点。
附图说明
图1为金属基底(如高压燃气轮机叶片)的横截面图,显示出根据本发明对两个粘合层都使用HVOF沉积方法涂覆的典型双层粘合层;
图2为显示涂于金属基底(用术语“基准”标明)的常规现有技术双层粘合层的横截面的显微照片,其中第一层使用HVOF喷涂涂覆,第二层使用APS;
图3为显示根据本发明的双层粘合层的第二种实施方案横截面的显微照片,其中双层涂层的两个层都用HVOF热喷涂涂覆,顶层包含约5wt%的聚酯;
图4为显示根据本发明的双层粘合层第三种实施方案的横截面的显微照片,其中双层涂层的两个层同样都用HVOF喷涂涂覆,顶层包含约15wt%的聚酯;和
图5为显示根据本发明的双层粘合层第四种实施方案的横截面的显微照片,双层的两个层都用HVOF涂覆,顶层包含约9wt%的聚酯。
具体实施方式
如上所述,根据本发明的双层粘合层包括第一致密内层和第二粗糙多孔外层,两个层都使用HVOF形成。通常,HVOF因其产生非常致密涂层的能力而只用于内粘合层。本发明通过喷涂金属粉末和聚酯粉末的粉末混合物在最外HVOF层内形成孔隙。具体地评价了约5-15wt%聚酯(以混合物的总重量计)的混合物,并且本发明考虑通过调整粉末尺寸使用直到约20%的聚酯掺入到涂层中,并通过包括添加剂以帮助聚酯在热喷涂过程中流动和分布。添加剂有助于提高聚酯在MCrAlY(如NiCrAlY)内的分散,从而防止聚集。也可通过在常规磨碎机中预混合(干混)涂层成分、通过喷雾干燥、或甚至通过使用角形聚酯粉末来获得改进的聚酯分散。这类技术有助于完全混合聚酯和McrAlY,当涂层被涂到基底时就使得聚酯更均匀地分散。混合还改善了热喷涂过程中的流动特性。
除了使用聚酯在最外HVOF层内建立所需水平的孔隙率外,本发明还考虑使用其它成分在最外层内实现孔隙率控制。这类成分可为碳粉末或其它线性聚合物或塑料,例如聚乙烯、聚苯乙烯或尼龙。
实施例1
根据本发明使用TAFA制造的JP5000 HVOF设备制造双层涂层。使用HVOF将利用Praxair Powder No.Ni211-17(Bal-Ni-22-Cr-10Al-1-Y)的NiCrAlY初始致密层一开始就涂到IN718基底(52Ni-19Fe-19Cr-5Nb-3Mo-1Ti)上。
然后通过喷涂NiCrAlY、Ni211-17和聚酯粉末即Metco 600NS粉末的混合物形成第二多孔层。Metco 600NS、Ni211和IN718都为市售材料。在使用HVOF喷涂完第二涂层后,制备金相试样并评价。检测证实,与较致密的内层相比,外层显示出提高的孔隙率。使用定量图象分析,测定外层的孔隙量为总层体积的约3-4%。
随后的试验评价其它比例的NiCrAlY/聚酯混合物。制造5、9和15wt%聚酯的混合物并评价,既进行金相学评价又使用炉循环测试。为了比较,还建立了常规HVOF/APS双层的基准体系。各种试验涂层的金相学比较结果在下面示于图1到5。
图1显示了根据本发明使用HVOF涂到基底上的典型双层涂层体系。涂到基底上的整个涂层包括绝热陶瓷层12、覆盖致密粘合层16的多孔粘合层14,16和14共同形成双层粘合层10。双层涂层又覆盖了形成汽轮机叶片基材的金属合金基底18。优选地,多孔粘合层14的厚度为约3-10密耳,致密粘合层16的厚度为约5-15密耳,双层粘合层10的厚度在8-25密耳的范围内。
图2至5显示了本发明的各种不同实施方案,即在使用HVOF热喷涂涂覆的第二较多孔层中具有不同的聚酯含量。各种实施方案的横截面的显微照片显示了从底部到顶部的相同层状结构,但在不同实施方案的外层(不太致密)中具有不同的聚酯含量。基础金属基底在图2至5中分别被表示为20、30、40和50。在图2至5中,第一致密HVOF层(提供耐氧化性)分别作为21、31、41和51出现;第二多孔层(具有不同的聚酯含量和可控密度)分别标示为22、32、42和52;顶部绝热陶瓷层分别显示为23、33、43和53。
在为汽轮机发动机高温部件时,基底18可由铁、镍或钴-基合金形成,但也可使用其它高温材料。陶瓷层12可通过等离子喷涂技术如空气等离子喷涂或真空等离子喷涂(也称为低压等离子喷涂(LPPS))来沉积。如上所述,陶瓷层12的优选材料为氧化钇稳定的氧化锆(YSZ),但也可使用其它陶瓷材料,包括用其它氧化物如氧化镁(MgO)、氧化铈(CeO2)或氧化钪(Sc2O3)稳定的氧化锆。
图1至5中显示的粘合层具有耐氧化性,从而能保护下面的基底不被氧化,同时能使等离子喷涂的陶瓷层13更牢固地粘着到粘合层上。另外,粘合层足够致密,但具有较低含量的氧化物,以进一步抑制基底的氧化。
下面的表1提供了根据本发明的各种HVOF/聚酯粘合层的对比评价。这个表提供了使用本发明的改进双层粘合层在TBC体系上进行炉循环试验FCT的结果,并将其与HVOF/APS双层涂层体系的“基准”比较。各种体系区别在于粘合层涂覆方法,而TBC部分对所有体系都不变。FCT试验为氧化性热循环试验。在具有自动升降系统的底部装载空气炉中进行试验,自动升降系统升高试样到热区,并交替地降低它们到冷却站,在冷却站,风扇引导室温空气经过试样。典型的循环由大约10分钟加热、在指定试验温度2000F下的45分钟停留时间和10分钟强制空气冷却组成,在冷却过程中,试样被冷却到400F以下。每天检查一次试样的TBC剥落,当剥落大于表面积的20%时中断试验,或在指定循环次数后停止试验。
HVOF双层体系的试验表明,具有9%聚酯的体系大约等价于基准体系。这种体系在N5上具有大于620次循环的寿命,在620次循环时中断FCT试验,在GTD111基底上时为420次循环。尽管这个试验没有说明HVOF双层超过基准系统的明确优越性,但它的确表明该体系具有进一步改进和提高的明显潜力。另外,通过利用单一方法HVOF涂覆致密层和多孔层两个层来简化加工的优点是本发明和常规粘合层体系之间的一个重要差别。
HVOF/聚酯粘合层的评价
体系标示 | %孔隙+氧化物 | FCT寿命,N5基底 | FCT寿命,GTD111基底 |
A:基准HVOF/APS(0%聚酯) | 19 | 620* | 620* |
B:HVOF/HVOF 5%聚酯 | 4.6 | 360 | 346 |
C:HVOF/HVOF 15%聚酯 | 44.1&7(随区域变化大) | 420 | 313 |
D:HVOF/HVOF 9%聚酯 | 6.75 | 620* | 420 |
在620次循环*时中断试验 |
尽管结合了现在认为最实用和优选的实施方案描述了本发明,但应认识到,本发明不限制于公开的实施方案,相反,而是旨在覆盖附加权利要求的精神和范围内包括的各种变更和等价方案。
部件列表
双层粘合层10
绝热陶瓷层12
等离子喷涂陶瓷层13
多孔粘合层14
粘合层16
金属合金基底18
致密的HVOF层16
Claims (10)
1.一种在燃气轮机发动机金属部件上使用的涂层体系,包括:
金属合金基底(18);
涂于所述合金基底(18)的双层粘合层(10),所述粘合层(10)具有由一种或多种包含铝或铬的金属间化合物组成的第一耐氧化层(16),和第二不太致密层(14),其由聚酯和包含铝和/或铬的一种或多种金属间化合物的粉末混合物形成,所述第一和第二层通过高速氧燃料(HVOF)热喷涂涂覆到所述合金基底(18)上;和
包含绝热陶瓷的顶层(12)。
2.如权利要求1所述的涂层体系,其中所述第一层(16)中的所述金属间化合物由MCrAlY组成,其中M为铁、钴或镍。
3.如权利要求1所述的涂层体系,其中所述第二层(14)中的所述一种或多种金属间化合物由MCrAlY组成,其中M为铁、钴或镍。
4.如权利要求1所述的涂层体系,其中所述第二层(14)中的所述聚酯的存在量为所述金属间化合物的5-20wt%。
5.如权利要求1所述的涂层体系,其中所述双层粘合层(10)的总厚度为约8-25密耳。
6.如权利要求1所述的涂层体系,其中所述第一耐氧化层(16)的厚度为约3-10密耳。
7.如权利要求1所述的涂层体系,其中所述第二不太致密层(14)的厚度为约5-15密耳。
8.在燃气轮机发动机金属部件上形成粘合层(10)的方法,包括步骤:
提供金属合金基底(18);
涂覆粘合层(10)到所述合金基底(18)上,其中使用高速氧燃料(HVOF)热喷涂将由一种或多种包含铝或铬的金属间化合物组成的第一耐氧化层(16)涂覆到所述合金基底(18)上,然后使用HVOF涂覆第二不太致密层(14),其由聚酯和一种或多种包含铝或铬的金属间化合物的粉末混合物形成;和
涂覆绝热陶瓷(12)到所述粘合层(10)上。
9.如权利要求8所述的方法,还包括在形成后热处理所述粘合层(10)的步骤,以在所述第一和第二层中扩散粘合颗粒。热处理还烧尽聚酯并在涂层中形成孔隙。
10.如权利要求8所述的方法,其中所述第二不太致密层(14)使用金属间化合物和聚酯的混合物来形成,聚酯的量为所述金属间化合物的5~20wt%。
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US20050260434A1 (en) | 2005-11-24 |
US7150921B2 (en) | 2006-12-19 |
JP2005330586A (ja) | 2005-12-02 |
EP1598439A3 (en) | 2006-05-17 |
EP1598439A2 (en) | 2005-11-23 |
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