IMR OpenIR
Cu−Zr−Ti块体金属玻璃及其与共晶反应之间的关系
代春丽
学位类型博士
导师卢柯
2008-01-09
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料学
关键词金属玻璃 玻璃形成能力 共晶反应 Cu基合金 内生复合材料
摘要具有“深共晶”特征的合金体系有利于形成金属玻璃。然而,对于三元以上的多组元合金,许多合金系尚缺乏完整可靠的相图,因此发展易于形成玻璃的合金主要依赖于“试错法”。尽管现已在许多三元合金中发现有可形成块体金属玻璃(BMGs)的成分,但BMG形成合金与相图中的共晶反应是否存在有必然的联系尚缺乏研究。澄清这种关系对于理解BMG形成的本质具有重要意义。在现已发现的BMG家族中,Cu基BMG以其高强度、高韧性、不含有贵金属和毒性元素等优越性展示出具有作为结构材料应用的前景。其中,Cu-ETM-M (ETM=Zr、Hf, M=Ti、Al、Ag)三元合金是Cu基BMG的化学成分基础。本工作选择Cu-Zr-Ti三元系,系统地研究了两个成分区域内合金的玻璃形成能力(GFA)对成分变化的依赖关系,以及相应的合金熔体凝固所经历的共晶反应。主要结论如下: 1. Cu-Zr-Ti三元系中,Cu60Zr30Ti10成分周围合金的GFA明显地依赖于成分的微量(如1 at.%)变化。最有利于形成BMG的成分为Cu60Zr33Ti7,可达到的临界直径(Dc)为4 mm。该合金位于相图中(L→Cu8Zr3+Cu10Zr7)单变共晶沟附近。相对于Cu-Zr二元系中的同一共晶反应,Ti元素的加入具有进一步稳定液相的作用,从而提高合金的GFA。 2. 以Cu60Zr33Ti7三元合金为基础,利用“3D”法,定位出Cu-Ag-Zr-Ti四元系中GFA最强的合金成分为Cu44.25Ag14.75Zr36Ti5(Dc=10 mm),是目前GFA最高的Cu基BMG之一。相对于Cu60Zr33Ti7三元合金,Ag的加入具有显著稳定液相的作用,从而更加有利于玻璃态的形成。 3. 具有高GFA的Cu44.25Ag14.75Zr36Ti5四元合金,熔体的凝固主要经历(L→Cu10Zr7+AgZr)伪二元共晶转变。Cu-Zr-Ti和Cu-Zr-Ag两个三元系中的BMG形成成分区域和Cu-Ag-Zr-Ti四元系中的BMG形成成分区域在三维成分空间上呈连续变化。Cu-Zr-Ag三元系中存在有(L→Cu10Zr7+AgZr)共晶转变,与之相关的具有最佳GFA的合金成分为Cu35.4Zr44.6Ag20 (Dc=3 mm)。 4. Cu-Zr-Ti三元系中,计算相图给出的(L→Cu10Zr7+CuZr+Cu2ZrTi)三元不变共晶点Cu52Zr40Ti8事实上偏离真正的共晶点,其熔体的凝固主要经历(L→Cu10Zr7 +CuZr)单变共晶反应。该合金周围成分区域的合金具有较强的GFA,至少有5个成分(间隔为1 at.%)点处合金的Dc可达到4 mm。这些合金大致沿着相图上的(L→Cu10Zr7 +CuZr)单变共晶沟,这一成分区域完全不同于Inoue等先前发现的Cu60Zr30Ti10合金(Dc=3 mm),表明在Cu-Zr-Ti三元系中至少存在有两个可形成BMG的成分区域。 5. Cu-Zr-Ti三元系中由CuZr、Cu10Zr7和Cu2ZrTi三相所围成的成分三角形区域内,在给定的熔体冷却速率下,合金成分由形成单一非晶相的成分区域向晶体相Cu10Zr7 和CuZr的成分两侧外延,可分别获得以Cu10Zr7 或CuZr作为初生晶体相、金属玻璃为基体的内生复合材料。在室温压缩载荷作用下,单相金属玻璃和含Cu10Zr7相复合材料几乎没有宏观塑性。而含CuZr相复合材料具有一定的塑性形变能力,塑性应变εp可达到4.2%。这与CuZr相自身的马氏体结构有关。
其他摘要Easy glass-forming alloy system usually has a “deep eutectic” feature. But for the ternary or multi-component alloys, phase diagrams of the systems are not always well-established in many cases. Therefore, it has to rely on the “trial and error” approach to develop easy glass formers. It is of interest to clarify the correlation between the BMG-forming composition and eutectic reaction, to understand the origin of the high glass-forming ability (GFA). Among the BMG families, the Cu-based BMGs have a potential application as new structural materials due to their high strength, assessable plasticity and excluding noble or toxic elements. Cu-ETM-M (ETM=Zr, Hf, M=Ti, Al) ternary alloys are the basic compositions of these Cu-based BMGs. In the present work, the Cu−Zr−Ti ternary system was selected to investigate the compositional dependence of BMG formation and the relation between GFA and eutectic reaction the alloy melt undergoes during solidification in two composition regions. The following conclusions are drawn: 1. Glass-forming ability of the alloys around the Cu60Zr30Ti10 composition in the Cu−Zr−Ti ternary system is strongly composition-dependent. The best glass former is Cu60Zr33Ti7 alloy with a Dc of 4 mm. This composition is near the univariant eutectic groove of (L→Cu8Zr3+Cu10Zr7). Compared with the CuZr binary BMGs related to the eutectic reaction of (L→Cu8Zr3+Cu10Zr7), the improvement of the glass-forming ability is caused by an effect that Ti significantly stabilizes the liquid. 2. Using the “3D pinpointing approach”, in the Cu-Ag-Zr-Ti quaternary system, Cu44.25Ag14.75Zr36Ti5 is discovered to have a Dc of 10 mm. Compared with the ternary alloy, the Ag addition plays a significant role in stabilizing the alloy melt. Such an effect is believed to be a main reason of improving GFA for the quaternary alloys. 3. The Cu44.25Ag14.75Zr36Ti5 alloy is a best glass former and solidification of its liquid upon cooling mainly undergoes a pseudo-binary eutectic reaction (L→Cu10Zr7+AgZr). The BMG-forming composition zones of the Cu−Zr−Ti and Cu-Zr-Ag ternary systems are linked with that of the Cu-Ag-Zr-Ti quaternary system in the 3D composition space. There exits a pseudo-binary eutectic reaction (L→Cu10Zr7+AgZr) in the Cu-Zr-Ag ternary system. Related to this eutectic reaction, the best glass former is Cu35.4Zr44.6Ag20 with Dc of 3 mm. 4. In the Cu-Zr-Ti ternary system, the Cu52Zr40Ti8 composition predicted using the CALPHAD calculation is not located at a ternary invariant eutectic point (L→Cu10Zr7+CuZr+Cu2ZrTi). Solidification of the Cu52Zr40Ti8 liquid upon cooling mainly undergoes a univariant eutectic reaction (L→Cu10Zr7+CuZr). Alloys around the Cu52Zr40Ti8 composition exhibit a GFA. Monolithic glassy rods of 4 mm in diameter can be fabricated under copper mould casting at least at five compositions, which are along the univariant eutectic groove of (L→Cu10Zr7+CuZr). The composition region is different from that previously reported by Inoue, indicating that more than two BMG-forming composition zones are present in this system. 5. In the Cu-Zr-Ti ternary system, the composition region bounded by the CuZr, Cu10Zr7 and Cu2ZrTi intermetallic, departure from the optimal composition range for glass formation, in situ composites comprised of metallic glassy matrix with Cu10Zr7 or CuZr as the primary phase can be fabricated. Under compression test at room temperature, the deformation and fracture of the monolithic glass and Cu10Zr7-containing composite is almost the same without any macroscopic plastic strain before failure. By contrast, the composites containing CuZr particles exhibit observed plastic strain around 4.2%. Such ductility results from the presence of the CuZr particles with martensitic structure.
页数135
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/16934
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
代春丽. Cu−Zr−Ti块体金属玻璃及其与共晶反应之间的关系[D]. 金属研究所. 中国科学院金属研究所,2008.
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