Determination of the melting and freezing temperatures of Pb nanoparticles embedded in a PbO–B2O3–SnO2glass by using only the SAXS method

Abstract

Melting and freezing of metallic nanoparticles embedded in glass matrices usually occur at temperatures lower than for the same metal in the bulk state.In situsmall-angle X-ray scattering (SAXS) measurements using a synchrotron beamline and a specially designed high-temperature chamber allowed the determination of the temperature dependence of the SAXS intensity produced by a dilute and nearly monodisperse set of spherical Pb nanoparticles, with an average radius 〈R〉 = 16.1 nm, embedded in a homogeneous lead–borate oxide glass. The temperature dependences of the nanoparticle volumeV(T) and nanoparticle radius of gyrationRg(T) derived from SAXS results exhibit clear discontinuities during the cooling and during the heating processes, thus allowing for precise determinations of the melting and freezing temperatures of the studied Pb nanoparticles. Additional features observed in bothV(T) andRg(T) curves showed that during the heating cycle the frozen Pb nanoparticles suffer a transition to a more compact phase at 433 K before melting at 580 K. The results of this work demonstrate that the melting and freezing temperatures of nanoparticles in a very diluted state – for which the X-ray diffraction technique is not sensitive enough – can be precisely determined by applying only the SAXS method.