Cluster-assembled metallic glasses
© Kartouzian; licensee Springer. 2013
Received: 9 July 2013
Accepted: 22 July 2013
Published: 30 July 2013
A bottom-up approach to nanofabricate metallic glasses from metal clusters as building blocks is presented. Considering metallic glasses as a subclass of cluster-assembled materials, the relation between the two lively fields of metal clusters and metallic glasses is pointed out. Deposition of selected clusters or collections of them, generated by state-of-the-art cluster beam sources, could lead to the production of a well-defined amorphous material. In contrast to rapidly quenched glasses where only the composition of the glass can be controlled, in cluster-assembled glasses, one can precisely control the structural building blocks. Comparing properties of glasses with similar compositions but differing in building blocks and therefore different in structure will facilitate the study of structure–property correlation in metallic glasses. This bottom-up method provides a novel alternative path to the synthesis of glassy alloys and will contribute to improving fundamental understanding in the field of metallic glasses. It may even permit the production of glassy materials for alloys that cannot be quenched rapidly enough to circumvent crystallization. Additionally, gaining deeper insight into the parameters governing the structure–property relation in metallic glasses can have a great impact on understanding and design of other cluster-assembled materials.
KeywordsBottom-up approach Metallic glasses Metal clusters
Metal clusters have been the subject of intensive investigations in the last three decades not only because they exhibit fascinating properties that largely differ from their atomic and bulk counterparts but also their size dependence and structure dependence provide unthinkable possibilities. Addition of a single atom may cause property alteration of appreciable magnitude [1–5]. Although metal clusters possess unique properties, the majority of their properties are not harvested mainly due to their high sensitivity to the surrounding environment. Metal clusters are usually produced and investigated under ultra-high vacuum conditions, which are hardly applicable outside modern research laboratories. Many innovative scientists have spelled out the desire to fabricate a new class of materials that are built from atomic clusters instead of individual atoms, in order to benefit from the unique properties of such clusters. In this respect, some examples are already realized [6–8] as so-called cluster-assembled materials (CAM).
Metallic glasses (MG) have also been studied extensively since the first amorphous metallic alloy was introduced more than half a century ago. By cooling with a high rate, Klement et al. observed the formation of glassy structure in a binary alloy Au75Si25. They also reported the instability of this material at room temperature. After discovery of bulk metallic glasses and hence the possibility to create amorphous structures with moderate cooling rates, various multicomponent alloys were found with high glass-forming ability. Many of these alloys are usable under normal conditions, and several industrial applications are currently realized [10–14]. Despite the intensive research in the field of MGs, the fundamental question about the correlation between their structure and their unique properties is yet to be answered. The major challenge to this end is rooted in the lack of a descriptive model for the structure of MGs. So far, their structures are merely considered as a collection of atoms without long-range order in contrast to crystalline materials. This definition fails to distinguish among various amorphous materials and leaves the separation to the composition of alloys.
Cluster-based models such as efficient cluster packing, cluster-plus-glue atom, and cluster resonance have already been suggested to describe the arrangement of atoms in metallic glasses. Many research groups have demonstrated the appositeness of these models through theoretical simulations in combination with experimental structure analysis [15–39]. In this context, metallic glasses are considered as a subcategory of CAMs.
Here, nanofabrication of metallic glasses through the bottom-up approach incorporating size-controlled metallic clusters is proposed.
Presentation of the hypothesis
Testing of the hypothesis
The first experiment of the kind should be performed on CuZr system based on the following reasoning. This system has been the subject of many experimental and theoretical studies in the past. Consequently, much is known about this binary system. Since only two metals are involved, generation of suitable binary clusters and their mass selection is easier compared to other multicomponent systems. In addition, CuZr alloys are known to be good glass formers over a range of compositions with glass transition temperature well above the room temperature [40–42]. The fact that both elements appear in more than one stable isotope, however, counts as a drawback. This makes the mass selection and cluster isolation more challenging.
Binary metal clusters can be generated using alloy targets. Ion beam techniques employed in the production of the metal clusters facilitate the use of high-resolution size selection filters. On the basis of the recorded mass spectra, the most intense mixed cluster should be isolated and deposited on a support material, which is kept at a temperature low enough to avoid crystallization of the film during deposition. It is expected that clusters with 13 atoms (CumZrn, n + m = 13) form icosahedra and thus benefit from enhanced structural stability. The composition of the most abundant mixed cluster may vary for different cluster sources and with source conditions. Particular care should be taken to avoid oxidation of metal clusters prior and during deposition. To assure the latter, cluster deposition should be performed under ultra-high vacuum conditions. Finally, the sample should be handled under controlled environment (e.g., inert gas) and below room temperature (to avoid postdeposition oxidation and crystallization) throughout the analysis process. The properties of the specific metal cluster or clusters (if a combination of them is used to produce the cluster film) can be investigated to gain knowledge on the structural building blocks. The optical, electronic, geometric, magnetic, and binding energies of metal clusters can be determined both theoretically and experimentally by state-of-the-art scientific instruments. In parallel experiments, a film of conventional metallic glass prepared through rapid quenching processes but with an identical composition as cluster film should be analyzed for comparison purposes. A constructive feedback loop between these two types of metallic glasses synthesized through bottom-up approach and conventional methods is of great importance to unravel fundamental uncertainties associated with structure-dependent properties of metallic glasses.
Implication of the hypothesis
Cluster-assembled metallic glass
This work was partially supported by The Royal Society in the form of a Newton International Fellowship.
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