CN109251053A - 用于陶瓷金属化和连接的空气钎焊填充材料和用于金属化和连接陶瓷表面的方法 - Google Patents
用于陶瓷金属化和连接的空气钎焊填充材料和用于金属化和连接陶瓷表面的方法 Download PDFInfo
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Abstract
提供一种活性空气钎焊填充材料,包含金属‑陶瓷混合物,所述金属‑陶瓷混合物包含优选其量的范围在约50至90 mol%之间的至少一种贵金属和优选其量的范围在约10至50 mol%之间的至少两种金属氧化物的固体混合物;特别地,所述固体混合物包含一种或多种铜氧化物CuOx,其中x的范围在0.5和1.0之间;和一种或多种过渡金属氧化物R”Oy,其中y的范围在1.0和3.0之间。
Description
优先权要求
本申请要求2017年7月14日提交的意大利专利申请号17181560.8的优先权,其公开内容通过引用结合于此。
技术领域
本发明涉及用于陶瓷金属化和连接的活性空气焊接填充材料。
特别地,本发明涉及适用于金属化和接合燃气轮机中的陶瓷部件诸如砖片(tile)的活性空气焊接填充材料的改进的组合物,例如以提供有效的热保护。
本发明还涉及用于金属化和连接陶瓷表面的方法,特别是用于将第一陶瓷表面接合到第二陶瓷或金属表面的方法。
背景技术
在许多技术领域中,例如在燃气轮机领域中,众所周知需要对在非常高温度下操作并且还暴露于特别恶劣的环境中(这使得部件承受高水平的应力,不仅有热应力还有腐蚀和机械应力)的部件/表面进行有效的热保护。
已知类型的高温TPS(热保护体系)基于陶瓷材料的使用,例如以施用于金属或陶瓷部件上的覆盖砖片形式。
钎焊是众所周知的将陶瓷(例如陶瓷砖片)连接在金属或其他陶瓷表面上的接合方法。
在钎焊中,将两件金属或一些选定的其他材料通过熔化并使钎焊填料流入接头而接合在一起。
特别是,空气钎焊是这样一种连接程序,其中陶瓷-陶瓷和陶瓷-金属件通过在空气中施用钎焊填料来接合,因此避免在保护气体气氛或在真空条件下操作,从而降低与该接合操作相关的生产成本。
最近,已经开发了所谓的“活性空气钎焊”(RAB)技术,其利用基于金属/金属氧化物的钎焊填料。例如,用于空气钎焊的钎焊填料是已知的,其包含贵金属(例如Ag)和铜氧化物(CuOx)。
RAB接头通常还在高温氧化条件下表现出优异的机械性能、热循环性能和长期稳定性。
然而,特别是在燃气轮机领域,已知的材料和技术并不完全令人满意。
适用于燃气轮机操作条件的陶瓷(在陶瓷或金属表面上)的钎焊实际上引起了特定的问题。
特别是,陶瓷的润湿是实现有效和持久连接的关键因素。除润湿外,还需要优异的抗氧化性和连接强度。
发明内容
因此,本发明的一个目的是提供一种用于陶瓷金属化和连接的空气钎焊填充材料,其适于克服现有技术的上述问题。
特别地,本发明的一个目的是提供一种与常规活性空气钎焊填料相比具有改进的性质和性能的材料,以便也适用于燃气轮机部件的热保护。
因此,本发明涉及如权利要求1中所定义的用于陶瓷金属化和连接的空气钎焊填充材料,并且涉及如权利要求11中所定义的用于陶瓷表面的金属化和连接的方法。
本发明的有利的优选特征是从属权利要求的主题。
基本上,本发明提供了一种用于陶瓷表面/部件的金属化和连接的改进的空气钎焊填充材料。
本发明的材料适用于宽范围的陶瓷表面(例如Al2O3、AlN、SiC)以提供优异的陶瓷-陶瓷和陶瓷-金属接头。
本发明的材料还可以在预处理金属化步骤中用作金属化层,接着用传统钎焊填料也就是常规非活性钎焊填料进行钎焊步骤。
与常规空气钎焊填料相比,本发明的材料提供了优异的润湿行为。
因此,与市售可得的空气钎焊接头相比,使用本发明的活性空气钎焊填充材料生产的陶瓷-陶瓷和陶瓷-金属接头表现出优异的润湿性。
此外,本发明的材料即使在高温(高于800℃)氧化气氛中也表现出改进的抗氧化性、优异的连接强度和不透气性以及长期稳定性。
因此,本发明的材料特别适用于钎焊高温部件(例如在燃气轮机中)以及密封材料(例如在固体-氧化物燃料电池(SOFC)、气体分离器、氧化物膜、传感器、热保护体系等中)。
本发明的活性空气钎焊填充材料可以易于加工并以糊膏、油漆,浆料、油墨等形式施用;或者以固体片的形式,特别是箔、片、线等施用。
由于在陶瓷表面上改进的润湿行为,本发明的材料特别适合用作金属化层并且还允许在不同材料之间制造气密密封。
广义而言,本发明的活性空气钎焊填充材料是金属-陶瓷混合物,所述金属-陶瓷混合物包含优选其量的范围在约50至90 mol%之间的至少一种贵金属和优选其量的范围在约10至50 mol%之间的至少两种金属氧化物的固体混合物。
在一个优选的实施方案中,本发明的活性空气钎焊填充材料是贵金属、第一金属氧化物R’Ox和第二金属氧化物R”Oy的三元合金体系。
因此,本发明的活性空气钎焊填充材料的一般组成为:
a M - b R’Ox - c R”Oy
其中:
M是贵金属,特别是银金属(Ag);
R’Ox是第一金属氧化物,特别是铜氧化物CuOx(即R’优选但不一定是Cu);
R”Oy是第二金属氧化物且具体是过渡金属氧化物,特别是CoOy、NiOy或FeOy,或内过渡金属氧化物,例如CeOy(即R”是过渡金属或内过渡金属,优选地但不一定选自Co、Ni、Fe、Ce);
a、b、c是M、R’Ox、R”Oy各自的摩尔分数;
x、y是氧化物R’Ox、R”Oy中各自的氧原子数。
优选地,贵金属是银(Ag)。
优选地,填充材料包含第一金属氧化物,其是铜氧化物CuOx,其中x的范围在0.5和1之间;和第二金属氧化物R”Oy,其为过渡金属氧化物(特别是:CoOy、NiOy、FeOy或其混合物)或内过渡金属氧化物(例如:CeOy),其中y的范围在1.0和3.0之间。
在优选的实施方案中,第二金属氧化物是CoOy,其中y的范围在1.0和3.0之间。
在优选的实施方案中,本发明的活性空气钎焊填充材料包含银金属(Ag)、铜氧化物(CuOx)和一种或多种过渡金属或内过渡金属的氧化物。
此处和下文中,术语“过渡金属”旨在还包括所谓的内过渡金属。
适用于本发明材料的过渡金属氧化物包括但不限于CoOy和CeOy。
根据本发明,通过加入至少一种第二活性金属氧化物(特别是Co、Ni、Fe或Ce的氧化物或其混合物)大大地改进了包含贵金属(特别是Ag)和第一氧化物(特别是铜氧化物)的钎焊填料,导致令人惊讶地改进的性能,特别是在陶瓷表面的增加的润湿性方面。
因此,本发明提供了一种改进的用于陶瓷表面金属化和连接的方法,特别是用于将第一陶瓷表面与第二陶瓷或金属表面接合。
基本上,本发明的方法包括以下步骤:
- 如前所述制备活性空气钎焊填充材料;
- 将活性空气钎焊填充材料施用于第一陶瓷表面上;
- 通过钎焊将第一陶瓷表面与第二陶瓷或金属表面接合。
根据本发明的一个方面,活性空气钎焊填充材料用于在陶瓷表面上形成薄金属化层。
为了将本发明的材料施用为金属化层,将选定量的粉末形式的材料成分(即贵金属M,例如Ag;和两种氧化物R’Ox,R”Oy)与至少一种溶剂、增塑剂或连结剂混合在一起以获得糊膏、丝网印刷油墨、油漆或喷雾浆料,可将其以薄层均匀分布在待处理的陶瓷部件的表面上(厚度为约10-50μm,优选约20μm或更少)。
因此,本发明的填充材料包含添加剂,以便形成糊膏、油漆、浆料或油墨;特别地,本发明的填料包含至少一种连结剂,特别是有机连结剂,诸如基于聚乙烯醇的有机连结剂或基于纤维素的有机连结剂;和/或至少一种溶剂和/或至少一种增塑剂。
在将活性空气钎焊填充材料施用到陶瓷表面上以形成金属化层之后,为了活化活性空气钎焊填充材料与陶瓷基础部件的化学结合,该金属化陶瓷部件例如通过使用在空气中操作的管式炉有利地预热至选定的温度T1,T1的范围在约800℃和1300℃之间,优选在约950℃和1050℃之间。
在金属化陶瓷表面的预处理/预热之后,可以使用各种常规钎焊填料合金诸如基于Ag(CB6、Ag-28Cu、Incusil-15、Incusil-10、Ag-21Cu-25Pd)和基于Cu的钎焊填料进行该预处理的陶瓷部件的接合。
根据本发明的另一方面,活性空气钎焊填充材料用于钎焊步骤,以形成陶瓷-陶瓷或陶瓷-金属接头。
在这种情况下,活性空气钎焊填充材料例如以糊膏、油漆、浆料、油墨等形式施用于第一陶瓷表面以形成钎焊层,该第一陶瓷表面可能如上所述进行了预处理以提供有金属化层,该钎焊层优选具有约100-300μm的厚度。
在其他实施方案中,本发明的活性空气钎焊填充材料是固体片的形式,特别是箔、片或线。并且活性空气钎焊填充材料以箔、片、线等形式用于钎焊步骤。
钎焊步骤有利地在约800℃至1300℃之间、优选约950℃至1050℃之间的范围的温度下进行,以便活化活性空气钎焊填充材料与陶瓷基础部件的化学结合。
本发明的材料可以有利地在直接原位进行的预备热处理工艺中通过金属M(例如Ag)、R’(例如Cu) 和R”(例如Co、Ni、Fe、Ce)的金属粉末的氧化以原位形成三元合金体系M-R’Ox-R”Oy来制备。
附图说明
参考附图在以下非限制性实施方案中通过示例进一步描述本发明,其中:
-图1是显示根据本发明的活性空气钎焊填充材料的DSC(差示扫描量热法)曲线的图;
-图2显示了分别用(a)常规空气钎焊填料和(b)根据本发明的活性空气钎焊填充材料处理的两个陶瓷表面的照片;
-图3是从用根据本发明的活性空气钎焊填充材料处理的金属化陶瓷基材记录的XRD(X-射线衍射)光谱;
-图4是从用根据本发明的活性空气钎焊填充材料处理的金属化陶瓷基材记录的BSE-SEM(背散射电子-扫描电子显微镜)图像。
-图5是用根据本发明的活性空气钎焊填充材料处理的陶瓷基材和钎焊区之间的界面的横截面二次电子显微照片。
具体实施方式
示例性材料通过称取特定量的银、铜氧化物和钴氧化物粉末来生产,且具体是:
Ag:50-90 mol%
CuOx:5-45 mol%
CoOy:5-45 mol%。
换而言之,制备三元体系a Ag-b CuOx-c CoOy,其中
a = 50-90,优选60-80,例如约70
b = 5-45,优选10-30,例如约20
c = 5-45,优选5-15,例如约10。
将粉末形式的组分混合以制备固体混合物(> 99.9%,325目)。
特别地,制备具有以下组成的示例性材料:
a Ag – b CuOx – c CoOy
其中:
x = 1; y = 1
a = 70, b = 20, c = 10。
在流动条件下使用在干燥氩气氛中操作的高温DCS装置通过热分析研究示例性材料的样品。
材料样品通过以10℃/min的速率升温至1100℃来加热,随后以相同的速率冷却至室温。
特别地,图1显示了示例性材料的DSC曲线。
值得注意的是,DSC分析未显示预期的偏晶反应L2 + O2→ CuO + L1的证据,其中L1和L2分别表示富Ag和富Cu的液相。
实际上,高于偏晶温度时,Cu作为Cu2O和CuO(即CuOx,其中x=0.5,1)的混合物存在。
第一个吸热峰归于以下反应:
Co3O4→ 3CoO + 1/2 O2。
第二个峰归于混合物氧化物CuO/CoO的形成并且第三个峰归于共晶熔融。
示例性材料(具有上述组成)的一些样品也与已知添加剂一起加入以形成糊膏,然后将其均匀地分布在氧化铝和氧化钇稳定的氧化锆(YSZ)的陶瓷表面上以形成厚度为约20μm或更小的薄金属化层。
根据上述DSC分析的相同温度循环通过在空气炉中对金属化陶瓷表面进行热处理来研究这些样品在陶瓷表面上的润湿行为。
为了比较,使用常规Ag-CuO20钎焊填料(即由80mol%银金属和20mol% CuO组成的二元体系)将相同的陶瓷表面金属化,然后在空气中进行相同的热处理。
如通过SEM分析,本发明材料和常规非活性钎焊填料在YSZ表面上的不同润湿行为的比较示于图2中。
图2比较了分别用以下物质处理的陶瓷表面(具体由YSZ-5 mol%HfO2制成)的两张微观照片:(a) 常规空气钎焊填料(具体是Ag-CuO,具有20mol%CuO)和(b) 根据本发明的三元活性空气钎焊填充材料(Ag-CuO-CoO,具有20mol%CuO和10mol%CoO)。将金属化陶瓷表面在1050℃下在空气炉中热处理10分钟。
与标准(非活性)Ag-CuO空气钎焊填料相比,本发明材料(除了Ag和CuO之外还包括CoO)的润湿性被证明是优异的。
通过预加热的金属化陶瓷表面的X射线衍射(XRD)分析和能量色散X射线(EDX)分析来研究在空气中热处理期间根据本发明的材料在陶瓷表面上的相演变。
组合的XRD和EDX分析检测了YSZ(即基材)、银(即活性空气钎焊填充材料的基质)和少量Co3O4和(Cu,Co)O的混合固溶体氧化物相(推测是Cu2CoO3)的存在。
例如,图3是从在1050℃下在空气中热处理10分钟之后用具有20 mol% CuO和10mol% CoO的本发明示例性材料Ag-CuO-CoO金属化的YSZ基材记录的XRD衍射图。
Co3O4和Cu2CoO3相是同构的,因此难以通过XRD区分。EDX分析证实了在金属化YSZ基材的预热的表面处存在(Cu,Co)O的混合固溶体氧化物相:Ag基质内的(Cu,Co)O相的相应背散射电子图像在图4中示出。
图4显示了在空气中在1050℃下热处理10分钟后从用Ag-CuO-CoO (20 mol% CuO,10 mol% CoO)金属化的YSZ基材记录的BSE-SEM图像。EDX分析证实了在Ag基质(图4中的白色区域)中(Cu,Co)O的混合固溶体氧化物相(图4中的深色粒子)的存在。
预热的金属化陶瓷表面(用本发明的材料金属化)的高温抗氧化性使用标准空气马弗炉在900℃的温度下研究。
检测到,根据本发明处理的钎焊样品基本上保持其重量,如经1600小时氧化时段所测量,即,没有明显的材料从金属化层损失,表明材料甚至在高温氧化环境中的长期稳定性。
最后,还研究了本发明的活性空气钎焊填充材料与常规钎焊填料相比的钎焊性能。
特别地,金属化陶瓷部件用本发明材料预处理并且在第一温度T1(范围在约800℃和1300℃之间,优选在约950℃和1050℃之间)下预热,然后使用市售可得的空气钎焊填料、特别是基于Ag的钎焊填料通过钎焊接合到金属或陶瓷部件。为此目的,将基于Ag的填料箔置于金属化陶瓷表面(根据本发明预处理)和金属或陶瓷部件之间,并在空气炉中加热至第二温度T2(优选低于T1,然而取决于所使用的空气钎焊填料,例如为1025℃)。
图5中示出了活性空气钎焊填充材料和陶瓷基材之间的界面区域的示例性横截面二次电子显微照片。
特别地,图5显示了由在富Ag基质中的(Cu,Co)O析出物(并且,取决于所使用具体空气钎焊填料的组成还有一些CuOx和CoOy析出物)得到的界面区域,基本上没有任何残余孔隙。大的白色区域由富银相得到,而较暗的区域是Cu和可能的Co的混合氧化物相。
通过使用根据本发明的活性空气钎焊填充材料在钎焊步骤中实际钎焊其他样品,获得类似的良好结果。
如上所述制备和测试其他样品,改变组分及其量,并且与常规的基于Ag-Cu的空气钎焊填料相比,在陶瓷基材上改进的润湿行为方面获得类似的性能。
认为在用本发明材料进行活性空气钎焊期间,(Cu,Co)O的混合固溶体氧化物相从共晶Ag-Cu-O液相析出并且因此活性氧化物(R“Oy)从共晶熔体取走了氧。这明显地导致该完全钎焊体系的润湿性增加,这可能与共晶熔体的较低表面张力有关。
事实上,过渡金属的其它活性氧化物诸如CeO2也显示出类似的特性,它们具有氧缓冲能力并在活性空气钎焊填充材料熔化期间释放氧。
最后,尽管已经结合上述优选实施方案说明了本发明,但是应该理解的是,在不偏离所附权利要求的范围的情况下,可以进行许多其他可能的修改和变化。
Claims (26)
1.活性空气钎焊填充材料,包含金属-陶瓷混合物,所述金属-陶瓷混合物包含至少一种贵金属和至少两种金属氧化物的固体混合物。
2. 根据权利要求1的材料,包含其量的范围在约50至90 mol%之间的至少一种贵金属和其量的范围在约10至50 mol%之间的至少第一和第二金属氧化物的固体混合物。
3.根据权利要求1或2的材料,其中所述固体混合物包含一种或多种铜氧化物CuOx,其中x的范围在0.5和1.0之间;和一种或多种过渡金属氧化物R”Oy,其中y的范围在1.0和3.0之间。
4.根据权利要求3的材料,其中所述固体混合物包含一种或多种选自CoOy、NiOy、FeOy、CeOy、其混合物的过渡金属氧化物R”Oy。
5.根据权利要求4的材料,包含CoOy,其中y的范围在1.0和3.0之间。
6.根据前述权利要求中任一项的材料,包含贵金属、铜氧化物和过渡金属氧化物的三元合金体系。
7.根据前述权利要求中任一项的材料,其中所述贵金属是银(Ag)。
8.根据前述权利要求中任一项的材料,包含一种或多种添加剂以便形成糊膏、油漆、浆料或油墨。
9.根据权利要求8的材料,包含至少一种连结剂;和/或至少一种溶剂和/或至少一种增塑剂。
10.根据权利要求1至7中任一项所述的材料,其为箔、片或线的形式。
11.用于陶瓷表面的金属化和连接的方法,特别是用于将第一陶瓷表面接合到第二陶瓷或金属表面的方法;所述方法包括以下步骤:
- 提供活性空气钎焊填充材料,包含金属-陶瓷混合物,所述金属-陶瓷混合物包含至少一种贵金属和至少两种金属氧化物的固体混合物;
- 将活性空气钎焊填充材料施用到第一陶瓷表面上;
- 将所述第一陶瓷表面钎焊到第二陶瓷或金属表面上。
12. 根据权利要求11的方法,其中所述活性空气钎焊填充材料包含其量的范围在约50至90 mol%之间的至少一种贵金属和其量的范围在约10和50 mol%之间的至少第一和第二金属氧化物的固体混合物。
13.根据权利要求11或12的方法,其中所述固体混合物包含一种或多种铜氧化物CuOx,其中x的范围在0.5和1.0之间;和一种或多种过渡金属氧化物R”Oy,其中y的范围在1.0和3.0之间。
14.根据权利要求13的方法,其中所述固体混合物包含一种或多种选自CoOy、NiOy、FeOy、CeOy、其混合物的过渡金属氧化物R”Oy。
15.根据权利要求14的方法,其中所述固体混合物包含CoOy,其中y的范围在1.0和3.0之间。
16.根据权利要求11至15中任一项的方法,其中所述活性空气钎焊填充材料包含贵金属、铜氧化物和过渡金属氧化物的三元合金体系。
17.根据权利要求11至16中任一项的方法,其中所述贵金属是银(Ag)。
18.根据权利要求11至17中任一项的方法,其中将活性空气钎焊填充材料施用于所述第一陶瓷表面上以形成金属化层;然后通过用另一种钎焊填料合金钎焊将金属化陶瓷表面接合于第二表面。
19.根据权利要求18的方法,其中所述活性空气钎焊填充材料以糊膏、油漆、浆料或油墨的形式施用以在所述第一陶瓷表面上形成厚度为约10-50μm、优选为约20μm或更小的所述金属化层。
20.根据权利要求18或19的方法,包括激活施用在第一陶瓷表面上的活性空气钎焊填充材料的步骤,所述激活步骤包括将所述第一陶瓷温度预热至第一温度。
21.根据权利要求20的方法,其中所述第一温度的范围在约800℃和1300℃之间,优选在约950℃和1050℃之间。
22.根据权利要求11至17中任一项的方法,其中所述活性空气钎焊填充材料用于所述钎焊步骤,以形成陶瓷-陶瓷或陶瓷-金属接头。
23.根据权利要求22的方法,其中将活性空气钎焊填充材料施用于所述第一陶瓷表面上以形成钎焊层,所述钎焊层优选具有约100-300μm的厚度。
24.根据权利要求22或23的方法,其中所述活性空气钎焊填充材料以箔、片、线等形式用于所述钎焊步骤。
25.根据权利要求22至24中任一项的方法,其中所述钎焊步骤在在约800℃至1300℃之间、优选在约950℃至1050℃之间的范围的温度下进行。
26.根据权利要求11至25中任一项的方法,其中在直接原位在所述第一陶瓷表面上进行的预备热处理工艺中通过所述至少一种贵金属和所述至少两种金属氧化物的相应金属粉末的氧化制备活性空气钎焊填充材料。
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CN105246861A (zh) * | 2013-06-05 | 2016-01-13 | 陶瓷技术有限责任公司 | 在陶瓷基材上的金属层 |
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CN101288928A (zh) * | 2008-05-09 | 2008-10-22 | 中国科学技术大学 | 陶瓷颗粒增强复合钎料 |
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