Investigation of Effect Mechanism of Hafnium and Zirconium in High Temperature Materials
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摘要: 在高温合金中,元素Hf和Zr可以促进γ+γ′共晶、MC(2)碳化物、M2SC碳硫化物和Ni5M相的形成,改变草书状MC和M3B2成为块状并且通过净化晶界或枝晶间自由态的S来提高这些薄弱部位的结合强度,从而延迟裂纹的形成和扩展。Hf和Zr可提高铸造高温合金室温拉伸和中温持久的强度和塑性。Hf,Zr抑制次生碳化物M23C6和M6C的生成,从而提高了合金在高温长时热暴露时的显微组织稳定性。Hf,Zr降低合金的初熔温度,Ni5Hf和Ni5Zr相的初熔被认为是Hf,Zr影响初熔的主要原因。通过1150℃/8h的预处理,Ni5Hf以Ni5Hf+γ(C)→MC(2)+γ反应或者固溶两种方式被消除。元素Hf可以缩小枝晶间失去毛细管补缩能力和固相线之间的温度范围,还能降低枝晶间液池沟通所需的液体量。在凝固后期枝晶间的富Hf熔体具有很好的流动性、浸润性和趋肤效应,这些都是降低合金热裂倾向、提高合金可铸性和焊接性能的有利因素。具有高的化学活性的富Hf液膜容易在铸件表面形成Hf2O薄层。Hf和Zr是钎焊用中间层合金的降熔点元素。根据凝固过程中富Hf,Zr熔体的成分最终发展出Ni-18.6Co-4.5Cr-4.7W-25.6Hf和Ni-10Co-8Cr-4W-13Zr两种中间层合金,使单晶高温合金的无Si、B连接成为现实。还发展出了定向凝固片状Ni3Al/Ni7Hf2共晶合金,成分为Ni-5.8Al-32Hf和Ni-4Al-26Hf-8Cr-4W。Ni-5.8Al-32Hf合金的最佳凝固条件为温度梯度G=250℃·cm-1和凝固生长速率R=5μm.s-1;Ni-4Al-26Hf-8Cr-4W,凝固条件为G=350℃·cm-1和R=1μm·s-1。Abstract: Hafnium and zirconium can promote the formation of (γ+γ′) eutectic,MC(2) carbides,M2SC sulfides and Ni5M phases in superalloys,change script MC and M3B2 into blocky shape and delay the initiation and propagation of cracks by cleaning the free state sulfur at grain boundary and interdendritic regions and strengthening their cohesion.Both of elements Hf and Zr increase the stress rupture strength and ductility of cast superalloys at intermediate temperature and also improve the tensile strength and ductility at room temperature.Hf and Zr strict the precipitation of secondary carbides,such as M23C6 and M6C,therefore stabilize the microstructure of alloys during long-term exposure at elevated temperature.However,Hf and Zr lower the incipient melting temperature of superalloys.The melting of Ni5Hf or Ni5Zr phases may be considered as one of the main factors affecting incipient melting.By means of a pretreatment at 1150℃/8h,Ni5Hf phase can be eliminated in two ways: The reaction Ni5Hf+ γ(C) →MC(2)+ γ or solid solution.Hafnium may narrow down the range between temperature lost the interdendritic capillary feeding action and solidus,as well as may decrease the liquid content necessary for linking the interdendritic pools in the late solidification.The Hf-rich melts in interdendritic zone have superior fluidity,wettability and skin effect.These are the factors in increasing castability and weldability of Hf-containing superalloys and in decreasing tendency of hot tear.The high chemical activity of skin Hf-rich liquid promotes the formation of a thin layer of Hf2O on the surface of castings.Hf and Zr are the melting point depressant in the interlayer alloys used for brazing.It may be considered that dendrites formed in the early solidification are brazed by interdendritic Hfor Zr-rich melts.Eventually,the Ni-18.6Co-4.5Cr-4.7W-25.6Hf and Ni-10Co-8Cr-4W-13Zr alloys were developed according to the composition of Hf-or Zr-rich melts,and the Si-or B-free-bonding for single crystal superalloys could be realized.Studying the Hf-rich melts also leads to the development of unidirectionally solidified lamellar Ni3Al/Ni7Hf2 eutectic.The suitable compositions for these eutectic in situ composites are Ni-5.8Al-32Hf and Ni-4Al-26Hf-8Cr-4W.The results showed that the lamellar Ni3Al/Ni7Hf2 eutectic aligned parallel to the direction of solidification were prepared with temparature gradient G=250℃·cm-1 and solidification rate R=5μm·s-1 for the ternary alloy,and G=350℃·cm-1 and R=1μm·s1 for multicomponent alloy.
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Key words:
- Superalloys /
- phase transformations /
- hafnium /
- zirconium /
- solidification /
- incipient melting /
- TLP bonding /
- Ni3Al/Ni7Hf2 eutectic /
- microstructure /
- MC(2) carbides /
- Ni5Hf phase /
- mechanical properties
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