CN1800425A - 修复镍基超合金的预制件和方法以及由此修复的元件 - Google Patents

修复镍基超合金的预制件和方法以及由此修复的元件 Download PDF

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CN1800425A
CN1800425A CNA2005101373537A CN200510137353A CN1800425A CN 1800425 A CN1800425 A CN 1800425A CN A2005101373537 A CNA2005101373537 A CN A2005101373537A CN 200510137353 A CN200510137353 A CN 200510137353A CN 1800425 A CN1800425 A CN 1800425A
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alloy
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S·萨蒂安
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Abstract

一种修复涡轮机的涡轮元件(10)的方法，以及在该方法中使用的烧结预制件(22，24)和由此修复的高γ’镍基超合金元件(10)。该烧结预制件(22，24)含有钴基钎焊合金和钴基耐磨合金粉末的烧结混合物。该钎焊合金构成烧结预制件(22，24)的至少约10－约35重量％，且含有熔点降低剂比如硼。该预制件(22，24)通过混合钎焊和耐磨合金粉末以形成粉末混合物，然后烧结该粉末混合物制成。为了使用该预制件(22，24)，将涡轮元件(10)的表面部分除去以露出次表面部分(20)，然后将预制件(22，24)扩散接合于次表面部分(20)以形成含有分散于耐磨合金基质的钎焊合金的耐磨修复材料。

Description

修复镍基超合金的预制件和方法以及由此修复的元件
技术领域
本发明一般涉及经受过度磨损的超合金构件，如燃气涡轮及其它涡轮机的元件。更特别地，此发明涉及一种修复由镍基超合金制成的，焊接时易产生裂纹的燃气涡轮机叶片的磨损表面的方法。
背景技术
超合金用于制造必须在高温下工作的元件，如工业燃气涡轮的叶片、喷嘴、燃烧器和变形接头。当这些元件在很高温度的条件下工作时，会发生各种损伤或损坏。例如，由于邻近喷嘴和叶片间摩擦接触，磨损和裂纹趋于在下一级叶片的角翼处发展。由于用超合金制成的元件成本相当高，典型地，比起更换它们，人们更希望修复这些元件。同样原因，由于制造缺陷而需要修复的新造元件也优先修复，而不是被报废。
已有的修复镍基超合金的方法包括气体保护钨极电弧焊(GTAW)技术。GTAW作为一种高热量输入工艺被人所知，它会在母体金属里产生热影响区(HAZ)并在焊接金属中产生裂纹。在GTAW修复中，典型地采用一种填料，所选填料材料典型地是一种延性填料或一种化学性质与母体金属相匹配的填料。采用延性填料的优点是减小产生裂纹趋势。用延性填料进行焊接修复的一个实例是采用IN617和IN625超合金修复磨损的叶片角翼，叶片用IN738和如GTD-111的等轴镍基超合金铸造。采用一种化学性质与母体金属相匹配的填料的显著优点是能更接近地保持超合金母体材料的预期性能。该方法的一个实例是用GTD-111或René80超合金制成的焊线焊接修复GTD-111超合金叶片。为了减小产生裂纹的可能性，母体金属典型地需要在高温下预热，如约700-930℃。采用两者中的任何一种方法，由于产生大的残余应力累积，GTAW工艺都会使母体金属变形。几何形状复杂的元件，如燃气涡轮机叶片，更不能承受变形，就此来说，GTAW可能并不是合适的修复方法，特别是若不能用延性填料。
更先进的定向凝固(DS)镍基超合金常不像GTD-111超合金易于焊接，而且增加了焊接金属和母体金属的HAZ中产生裂纹的危险。一个突出的实例是镍基超合金GTD-444，由于其满意的抗蠕变性能，已经发现它可用于先进工业燃气涡轮上的后几级(如，二或三级)叶片。GTD-444不易于焊接主要是因为其较高的伽马撇(γ′)含量(约55-59％)，而且先前的焊接尝试曾在母体金属HAZ和焊接金属中产生无法接受的裂纹。
根据以上所述，需要另一种修复方法来修复高γ′镍基超合金以达到无裂纹修复。为了修复该超合金的易磨损表面，也需要修复金属同样表现出良好的磨损性能。一个这种方法称为活性扩散修复(ADH)，一般指定的美国专利5902421和6530971披露了该方法的实例。ADH工艺用了一种合金粉末或粉末混合物，该粉末将在比所要修复的超合金元件低的温度下熔化。如果组合两种粉末，其中将一种粉末配制成比另一种粉末在低得多的温度下熔化，以便熔化时形成两相混合物。真空钎焊使钎焊粉末混合物熔化并和待修复元件的超合金一起形成合金。接着进行二次钎焊扩散热处理循环以进一步促进相互扩散，这提高了钎焊混合物的重熔温度。
另一种可选修复方法在Hasz等人的一般指定的美国专利6398103中披露，它涉及将耐磨金属箔钎焊到元件的磨损表面。该金属箔通过将耐磨材料热喷涂在承载板上制成。合适的耐磨材料包括碳化铬材料和Co-Mo-Cr-Si合金，如市售的TRIBALOYT400和T800合金。还有另一种方法在一般指定的美国专利申请10/708205披露，它涉及采用通过烧制在粘结剂中含钎焊材料和耐磨合金的粉末的柔韧板材制成的钎焊条。将该焊条施加于修复表面，然后进行热处理使钎焊条扩散接合于修复表面，以便确定焊敷表面，随后加工至修复所需的尺寸。
随着更多高度合金化的超合金的出现，需要专门用于特殊修复表面的改进修复方法和材料，包括超合金和修复所需的强度和微观结构。一个突出的实例是需要专门在具有复杂形状、由高γ′含量的超合金例如GTD-444制成的元件上实施修复的材料和方法。
发明内容
本发明提供了一种能够修复涡轮机涡轮元件表面的方法，以及用于该方法的烧结预制件和用该工艺修复的涡轮元件。该方法和预制件特别适合修复高γ′含量的镍基超合金制成的涡轮元件，其中一个特别实例是GTD-444超合金。本发明的方法可以在足够低至使变形最小化的温度下进行，其特别有利于修复复杂形状，如工业燃气涡轮叶片的角翼。
本发明所用烧结预制件基本上由钴基钎焊合金和钴基耐磨合金粉末的烧结混合物组成。钴基钎焊合金构成烧结预制件的至少约10-约35重量％，而且含有足量的硼以使钴基钎焊合金熔点为约2000°F-约2230°F(约1090℃-约1220℃)。
一种采用烧结预制件修复燃气涡轮涡轮元件的方法涉及通过混合上述钴基钎焊合金和钴基耐磨合金的粉末形成粉末混合物，混合物中至少约10-约35重量％为钴基钎焊合金，然后烧结粉末混合物以形成烧结预制件。预制件的使用包括除去涡轮元件的表面部分以露出涡轮元件的次表面部分，接着将烧结预制件扩散接合到涡轮元件的次表面部分以形成由分散在耐磨钴基合金基质中的钴基钎焊合金组成的耐磨修复材料。随后，可以加工修复材料以获得所需的最终尺寸和表面性能。
所得的修复的涡轮元件优选是镍基超合金，其含有在使用气体钨弧焊时易于使涡轮元件产生裂纹的组成和γ′含量。该修复的涡轮元件特征在于具有耐磨修复材料扩散接合于此的区域，其中耐磨修复材料由分散在耐磨钴基合金基质材料中的钴基钎焊合金组成。
根据以上所述可见，本发明提供了一种修复先进镍基超合金的方法和材料，该镍基超合金在试图被焊接修复时，特别是使用的填料材料性能与母体金属相似时，易于产生裂纹。本发明使用了扩散接合循环而不是焊接，这避免了由焊接导致的热应力和变形，而且获得比用延性填料材料进行焊接修复时性能更接近母体金属性能的修复区。
本发明的其它目的和优点将从以下的详述中更好地体现。
附图说明
图1是预备根据本发明的修复方法修复的三段式叶片铸件的侧视图。
图2和图3表示适于修复图1叶片的烧结预制件。
具体实施方式
图1表示一种用于工业燃气涡轮机的涡轮部分的三段式涡轮叶片10。该叶片10用最终加工前的铸件表示，其包括从根部14延伸的机翼12。各种高温材料都可以用于制成叶片10，值得注意的例子包括商业上已知的GTD-111和GTD-444镍基超合金。本发明特别涉及由具有高γ’含量的高合金化镍基超合金，比如GTD-444制成的元件，其公称组成以重量百分数计为：约9.5-10％铬，约7-8％钴，约3.35-3.65％钛，约4.1-4.3％铝，约5.75-6.25％钨，约1.30-1.705钼，约4.60-5.0％钽，约0.06-0.1％碳，约0.0080-0.010％锆，约0.008-0.0105％硼，余量为镍和附带的杂质。GTD-444配制成定向凝固(DS)合金，且具有高γ’含量(约55-59％)。超合金比如GTD-444的γ’含量高，使得超合金在试图被实施焊接修复时容易产生裂纹。本发明也涉及修复几何形状复杂、因而试图进行焊接修复时容易变形的镍基超合金元件。当由GTD-444制成时，图1中描述的叶片10即是两种复杂环境的实例，特别是在围绕角翼16的区域，其复杂的几何形状很容易因焊接而变形。
正如本领域中所知，设置角翼16是为了密封装有叶片10的燃气涡轮的邻近的喷嘴段(未示出)。每一翼16终止于经受由于在邻近喷嘴上与密封件摩擦接触而损坏的尖端18。尖端18与喷嘴之间的接触特征在于由于制造误差、不同的热膨胀率、涡轮操作期间的动力学因素而带来的高压力和相对运动。因此，角翼16和它们的尖端18很容易产生那些必需修复的损伤。为了此目的，示出的叶片10在其根部14除去了表面区域，露出了次表面区域20该区域在叶片10的一侧包括两个角翼16。因此，图1表示了叶片10修复方法的第一步，通过此可以除去翼16的破损或损坏的部分。
图2描述了裁减和成形以代替图1中被除去以暴露次表面区域20的母材的烧结预制件22。被设计只用于修复角翼16的尖端18的预制件24在图3(所示比例与图1和2不同)中描述。根据本发明，预制件22和24含有最高约90重量％的耐磨钴基合金，且余量基本是含有熔点降低剂，优选硼的，钴基钎焊合金以便处于母体超合金的再结晶温度以下时能使预制件22和24扩散接合于叶片10，该温度对于GTD-444为约1230℃。正如此处所用，术语钴基定义为主要成分为钴的合金。该钎焊合金的性质优选包括熔化温度最高约1220℃，与GTD-444兼容，中等耐磨性，硬度和抗氧化性，可加工性，和低产生裂纹倾向。优选的钎焊合金基于商业上已知的超合金Mar M 509B，其具有公称组成，以重量计，为约24％铬，约10.8％镍，约7.5％钨，约4％钽，约0.25％钛，约2.7％硼，约0.6％碳。余量为钴和附带的杂质。本发明钎焊合金成分的合适的组成范围，以重量计，约22.00-约24.75％铬，约9.0-约11.0％镍，约6.5-约7.6％钨，约3.0-4.0％钽，约2.60-3.16％硼，约0.55-约0.65％碳，约0.15-0.30％钛，约0.30-0.60％锆，最高1.3％铁，最高0.4％硅，最高0.10％锰，最高0.015％硫，和余量钴和附带的杂质。
由于在预制件22和24中存在钎焊合金，耐磨合金的熔化温度尽管低于GTD-444母体金属，但可能会超过该钎焊合金，例如高于1090℃但低于1315℃。该耐磨合金的性能优选包括与GTD-444兼容，低的产生裂纹趋势，中等耐磨性，硬度，和抗氧化性和可加工性。基于商业上已知硬质表面材料的两种钴合金经本发明认定适于用作耐磨合金。第一种基于由Deloro Stellite有限责任公司市售的，名称为TRIBALOYT800的钴基合金。该T800型合金含有，以重量计，约27-约30％钼，约16.5-约18.5％铬，约3.0-约3.8％硅，最高1.5％铁，最高1.5％镍，最高0.15％氧，最高0.03％硫，最高0.03％磷，和最高0.08％碳，余量钴和附带的杂质。在此发明中使用的T800型耐磨合金的优选组成，以重量计，为约29％钼，约18％铬，约3.5％硅，约0.08％碳，余量钴和附带的杂质。第二种适合用作此发明的耐磨合金基于由不同来源市售的，名称为CM64型的钴合金，其中的例子来源于Deloro Stellite有限责任公司，名称为STELLITE694。CM64型耐磨合金的合适组成，以重量计，为约26.0-约30.0％铬，约18.0-约21.0％钨，约4.0-约6.0％镍，约0.75-约1.25％钒，约0.7-约1.0％碳，最高3.0％铁，最高1.0％锰，最高0.5％钼，最高1.0％硅，最高0.05％硼，余量钴和附带的杂质。CM64型合金的优选组成，以重量计，约28％铬，约19.5％钨，约5％镍，约1％钒，约0.85％碳，余量钴和附带的杂质。
预制件22和24通过混合钎焊和耐磨合金的粉末制成。该钎焊和耐磨合金粉末的合适的颗粒尺寸为325目大小。钎焊合金以能够将耐磨合金和叶片10的母体金属通过硼扩散进行冶金连接的量存在于预制件22和24。预制件22和24中钎焊合金含量的低限为约10重量％以将该预制件的孔隙率限制在可接受的范围。超过预制件22和24的约35重量％，该钎焊合金会不良地降低修复的机械和环境性能。在优选实施方案中，预制件的钎焊合金含量为约15重量％。除了钎焊和耐磨合金，预制件22和24的制造中不需要其它组分。
混合后，将该粉末进行烧结以使制成的预制件22和24具有良好的结构强度和低孔隙率，优选低于2体积％。在烧结期间，该粉末被压缩以促进熔化和降低预制件22和24的孔隙率。基于优选含有约15重量％钎焊合金的预制件组成，预制件22和24(和由预制件22和24制成的修复件)具有下列名义组成(不包括附带的杂质)。
  T800型预制件   CM64型预制件
  CrNiWTaTiMoSiFeVBCCo   18.5％0.920.640.340.02126.53.20.230.12余量(约49.5％)   27.6％5.518.90.360.0232.70.910.240.87余量(约42.8％)
在作为本发明准备的研究中，基本为图1所示类型并由GTD-444超合金制成的定向凝固叶片通过放电加工机(EDM)加工到深度为约0.1英寸(约2.5mm)以除去根部的表面区域，基本如图1所示。在EDM后，将暴露区域研磨以完全除去EDM期间形成的重铸层，然后用丙酮清洗。然后将暴露区域用由Wall Colmonoy公司市售的，名称为NicroBlast的镍—铬—铁粗砂进行喷丸处理。实施喷丸处理操作以清洁暴露区域，在表面产生压应力以加强可钎焊性能，并且沉积能加强暴露区域润湿性的光滑的镍涂层。NicroBlast粉末具有-60目的颗粒尺寸，但是也可预见性地使用更小或更大颗粒尺寸。
对于该研究，评价了两种不同的预制件配方。该配方含有约15或者约10重量％的钎焊合金，余量分别为上述T800型或CM64型耐磨合金。更特别地，该钎焊合金具有公称组成，以重量计，约24％铬，约10.8％镍，约7.5％钨，约4％钽，约0.25％钛，约2.7％硼，约0.6％碳，余量钴和附带的杂质。所用的T800型耐磨合金具有公称组成，以重量计，约29％钼，约18％铬，约3.5％硅，约0.08％碳，余量钴和附带的杂质。CM64型耐磨合金具有公称组成，以重量计，约28％铬，约20％钨，约5％镍，约3％铁，约1％钒，约0.9％碳，余量钴和附带的杂质。
然后将粉末混合并在模具中烧结以生产厚度为约0.1英寸(约2.5mm)，孔隙率小于2体积％的预制件。在用喷水和EDM切割预制件以获得与图2所示相似的外形后，将预制件定位焊至叶片的暴露表面区域。
将预制件用两种真空热处理中的一种扩散接合至暴露表面区域。对含有T800型耐磨合金预制件的热处理包括以约25°F/分钟(约14℃/分钟)的速率加热至约1200°F(约650℃)的均热温度保持约30分钟，以约25°F/分钟的速率加热至约1800°F(约980℃)的均热温度保持约30分钟，以约35°F/分钟(约20℃/分钟)的速率加热至约2210°F(约1210℃)的最高均热温度保持约20分钟，炉冷至温度约2050°F(约1120℃)，并保持约60分钟，炉冷至温度约1500°F(约815℃)，最后冷却至室温。除了采用的最高均热温度为约2240°F(约1227℃)外，含有CM64型耐磨合金的预制件的热处理循环基本相同。热处理后将所有的修复件加工至近似所需尺寸特征。
一些修复角翼的金相截面表明修复件非常均匀，且整个连接界面无孔隙，具有良好的冶金结合。其它修复叶片通过荧光渗透检验(FPI)进行无损检测，明显地该修复件和底层超合金母体金属无裂纹产生。
在接下来的研究中，由GTD-444制成的叶片尖端用含有约15重量％的钎焊合金和余量为T800型耐磨合金的预制件配方进行修复。在基本与上述对前述含有T800型耐磨合金的预制件配方相同的钎焊热处理以后，叶片无裂纹产生，且所得的修复件比最初的GTD-444材料具有更好的耐磨性。
虽然已经根据特殊的实施方案对本发明进行了描述，但是显然本领域的技术人员可以采用其它形式。因此，本发明的范围仅仅通过下面的权利要求限定。
10叶片
12机翼
14根部
16翼
18尖端
22预制件
24预制件
20区域。

Claims (10)

1、一种烧结预制件(22，24)，其包括钴基钎焊合金和钴基耐磨合金粉末的烧结混合物，该钴基钎焊合金构成烧结预制件(22，24)的约10-约35重量％，并含有足量的硼以使该钴基钎焊合金具有约1090℃-约1230℃的熔点。
2、如权利要求1的烧结预制件(22，24)，特征在于该钴基钎焊合金，以重量计，由约22.00-约24.75％铬，约9.0-约11.0％镍，约6.5-约7.6％钨，约3.0-4.0％钽，约2.60-3.16％硼，约0.55-约0.65％碳，约0.15-0.30％钛，约0.30-0.60％锆，最高1.3％铁，最高0.4％硅，最高0.10％锰，最高0.015％硫，余量钴和附带的杂质组成。
3、如权利要求1和2中任一项的烧结预制件(22，24)，特征在于该钴基耐磨合金，以重量计，由约27-约30％钼，约16.5-约18.5％铬，约3.0-约3.8％硅，最高1.5％铁，最高1.5％镍，最高0.15％氧，最高0.03％硫，最高0.03％磷，最高0.08％碳，余量钴和附带的杂质组成。
4、如权利要求1-3中任一项的烧结预制件(22，24)，特征在于该钴基耐磨合金，以重量计，由约26.0-约30.0％铬，约18.0-约21.0％钨，约4.0-约6.0％镍，约0.75-约1.25％钒，约0.7-约1.0％碳，最高3.0％铁，最高1.0％锰，最高0.5％钼，最高1.0％硅，最高0.05％硼，余量钴和附带的杂质组成。
5、一种燃气涡轮的修复的涡轮元件(10)，该涡轮元件(10)由镍基超合金制成，该超合金具有当经受气体保护钨极电弧焊时会使涡轮元件(10)产生裂纹的组成和γ’含量，该涡轮元件(10)具有耐磨修复材料扩散接合于此的修复区域，该耐磨修复材料由分散于耐磨钴基合金基质材料中的钴基钎焊合金组成。
6、如权利要求5的修复的涡轮元件(10)，特征在于该耐磨修复材料的公称组成，以重量计，由约18.5％铬，约0.92％镍，约0.64％钨，约0.34％钽，约0.23％硼，约0.12％碳，约0.021％钛，约26.5％钼，约3.2％硅，余量钴和附带的杂质组成。
7、如权利要求5和6中任一项的修复的涡轮元件(10)，特征在于该耐磨修复材料的公称组成，以重量计，由约27.6％铬，约5.5％镍，约18.9％钨，约0.36％钽，约0.24％硼，约0.87％碳，约0.023％钛，约2.7％铁，约0.91％钒，余量钴和附带的杂质组成。
8、如权利要求5-7中任一项的修复的涡轮元件(10)，特征在于该镍基超合金，以重量计，由约9.5-约10％铬，约7-约8％钴，约3.35-约3.65％钛，约4.1-约4.3％铝，约5.75-约6.25％钨，约1.30-约1.70％钼，约4.60-约5.0％钽，约0.06-约0.1％碳，约0.0080-约0.010％锆，约0.008-约0.0105％硼，余量镍和附带的杂质组成。
9、一种修复燃气涡轮的涡轮元件(10)的方法，该方法包括步骤：
将钴基钎焊合金和钴基耐磨合金的粉末混合以形成粉末混合物，该钴基钎焊合金构成粉末混合物的约10-约35重量％和含有足量的硼以使该钴基钎焊合金具有约1090℃-约1230℃的熔点；
烧结该粉末混合物以形成烧结预制件(22，24)；
将涡轮元件(10)的表面部分除去以露出涡轮元件(10)的次表面部分(20)；然后
将烧结预制件(22，24)扩散接合于涡轮元件(10)的次表面部分(20)以形成由分散于耐磨钴基合金基质中的钴基钎焊合金组成的耐磨修复材料。
10、如权利要求9的方法，还包括在扩散接合步骤前将含镍涂层沉积在涡轮元件(10)次表面部分(20)的步骤。
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