Synthesis and Characterization of Two Component Alloy Nanoparticles
Ajayan, Pulickel M.
Doctor of Philosophy
Alloying is an old trick used to produce new materials by synergistically combining at least two components. New developments in nanoscience have enabled new degrees of freedom, such as size, solubility and concentration of the alloying element to be utilized in the design of the physical properties of alloy nanoparticles (ANPs). ANPs as multi-functional materials have applications in catalysis, biomedical technologies and electronics. Phase diagrams of ANPs are very little known and may not represent that of bulk picture, furthermore, ANPs with different crystallite orientation and compositions could remain far from equilibrium. Here, we studied the synthesis and stability of Au-Sn and Ag-Ni ANPs with chemical reduction method at room temperature. Due to the large difference in the redox potentials of Au and Sn, co-reduction is not a reproducible method. However, two step successive reductions was found to be more reliable to generate Au-Sn ANPs which consists of forming clusters in the first step (either without capping agent or with weakly coordinated surfactant molecules) and then undergoing a second reduction step in the presence of another metal salt. Our observation also showed that capping agents (Cetrimonium bromide or (CTAB)) and Polyacrylic acid (PAA)) play a key role in the alloying process and shorter length capping agent (PAA) may facilitate the diffusion of individual components and thus enabling better alloying. Different molar ratios of Sn and Au precursors were used to study the effect of alloying elements on the melting point and the crystalline structures and melting points were determined by various microscopy and spectroscopy techniques and differential scanning calorimetry (DSC). A significant depression (up to150°C) in the melting transition was observed for the Au-Sn ANPs compared to the bulk eutectic point (T m 280°C) due to the size and shape effect. Au-Sn ANPs offer a unique set of advantages as lead-free solder material which can reflow at lower temperatures leading to lower thermal stresses in adjacent electronic components during the manufacturing process, offering better thermal and mechanical properties suitable for high temperature electronic applications. The second system studied here is Ag-Ni ANPs and electron microscopy and spectroscopy confirm the formation of Ag 0.5 Ni 0.5 ANPs with cubic structure, stable up to125°C. Atomic size and crystalline structure have less effect on the alloy formation process at the nanoscale; therefore, metals with limited solubility in bulk could form solid solutions at the nanoscale. Ag and Ni are immiscible in both solid and liquid states due to the large lattice mismatch and thermodynamically, the formation of core-shell structures is favoured. The effect of capping agents on the alloying was also studied here. Polyvinyl alcohol (PVA) with shorter length shows Ag-Ni ANPs with higher content of Ni compared to sodium citrate; the systems lead to the formation of Ag, Ag 2 O 2 and Ag 0.5 Ni 0.5 ANPs. The study of multi-component nanoparticle systems could shed light into the various parameters that affect stability of structure and phases, which could be quite distinct from their bulk counterparts.
Applied sciences; Alloy nanoparticles; Gold nanoparticles; Materials science