Flexible multiferroic 0–3 composite films, comprising NiFe2O4 and CoFe2O4 ferrite nanoparticles in a polyvinylidene fluoride (PVDF) matrix, have been prepared by solvent casting and melt crystallization to investigate the polymer β-phase nucleation mechanism. Infrared spectroscopy confirms the nucleation of the polymeric electroactive β-phase with the addition of both ferrites, although the loading of ferrite nanoparticles needed to obtain the highest amount of β-phase was found to be one order of magnitude higher in the NiFe2O4/PVDF nanocomposites. Transmission electron microscopy imaging and thermogravimetric analyses indicate the formation of an interface in the nanocomposites with the β-phase nucleation. It is shown that the essential factor for the nucleation of the β-phase in the ferrites/PVDF nanocomposites is the static electric interaction between the magnetic particles with a negative zeta potential and the CH2 groups having a positive charge density.
26 June 2012 in The Journal of Physical Chemistry C
This work reports on the nucleation of the β-phase of poly(vinylidene fluoride) (PVDF) by incorporating CoFe2O4 and NiFe2O4 nanoparticles, leading in this way to the preparation of magnetoelectric composites. The fraction of filler nanoparticles needed to produce the same β- to α-phase ratio in crystallized PVDF is 1 order of magnitude lower in the cobalt ferrite nanoparticles. The interaction between nanoparticles and PVDF chains induce the all-trans conformation in PVDF segments, and this structure then propagates in crystal growth. The nucleation kinetics is enhanced by the presence of nanoparticles, as corroborated by the increasing number of spherulites with increasing nanoparticle content and by the variations of the Avrami’s exponent. Further, the decrease of the crystalline fraction of PVDF with increasing nanoparticle content indicates that an important fraction of polymer chains are confined in interphases with the filler particle.
In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag–Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a “glass-float” (ukidama) structure.
Magnetophoresis\char22{}the motion of magnetic particles under applied magnetic gradient\char22{}is a process of great interest in novel applications of magnetic nanoparticles and colloids. In general, there are two main different types of magnetophoresis processes: cooperative magnetophoresis (a fast process enhanced by particle-particle interactions) and noncooperative magnetophoresis (driven by the motion of individual particles in magnetic fields). In the case of noncooperative magnetophoresis, we have obtained a simple analytical solution which allows the prediction of the magnetophoresis kinetics from particle characterization data (size and magnetization). Our comparison with new experimental results shows good quantitative agreement. In addition, we show the existence of a universal curve onto which all experimental results should collapse after proper rescaling. The range of applicability of the analytical solution is discussed in light of the predictions of a magnetic aggregation model [Soft Matter 7, 2336 (2011)].
1 February 2013 in Journal of Non-Crystalline Solids