Quartz crystal microbalance study of the kinetics of surface initiated polymerization

Surface initiated polymerization (SIP) is a valuable tool in synthesizing functional polymer brushes, yet the kinetic understanding of SIP lags behind the development of its application. We apply quartz crystal microbalance (QCM) to address two issues that are not fully addressed yet play a central role in the rational design of functional polymer brushes, namely quantitative determination of the kinetics and the initiator efficiency (IE) of SIP. SIP are monitored online using QCM. Two quantitative frequency-thickness (f-T) relations make the direct determination and comparison of the rate of polymerization possible even for different monomers. Based on the bi-termination model, the kinetics of SIP is simply described by two variables, which are related to two polymerization constants, namely a = 1/(k (p,s,app)-[M][R center dot](0)) and b = k (t,s,app)/(k (p,s,app)[M]). Factors that could alter the kinetics of SIP are studied, including (i) the molecular weight of monomers, (ii) the solvent used, (iii) the initial density of the initiator, (iv) the concentration of monomer, [M], and (v) the catalyst system (ratio among the ingredients, metal, ligands, and additives). The dynamic nature of IE is also described by these two variables, IE = a/(a + bt). Instead of the molecular weight and the polydispersity, we suggest that film thickness, the two kinetic parameters (a and b), and the initial density of the initiator and IE be the parameters that characterize ultra-thin polymer brushes. Besides the kinetics study of SIP, the reported method has many other applications, for example, in the fast screening of catalyst system for SIP and other polymerization systems.

Electrochemical polymerization and characterization of polypyrrole nanowires and nanotubules

Polypyrrole nanostructure arrays, including simultaneously large quantities of nanowires and small quantities of partially filled nanotubules have been electrochemically synthesized in home-made etched ion-track polycarbonate (PC) templates. Diameter of the prepared nanostructures varies from 45 to 320 nm with their lengths up to 30 microns. Morphological studies of these nanostructures were performed by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. While optical absorption properties were studied by ultraviolet-visible-near infrared spectrophotometry (UV-vis-NIR). It has been observed that the absorption maximum of polypyrrole shifts to the longer wavelength side as the diameter of these nanostructures (nanowires and nanotubules) increases. (C) 2010 Elsevier B.V. All rights reserved.