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.

Surface Plasmon Resonances of Cu Nanowire Arrays

Surface plasmon resonances of arrays of parallel copper nanowires, embedded in ion track-etched polycarbonate membranes, were investigated by systematic changes of nanowires’ topology and arrays area density. The extinction spectra exhibit two peaks which are attributed to interband transitions of Cu bulk metal and to a dipolar surface plasmon resonance, respectively. The resonances were investigated as a function of wire diameter and length, mean distance between adjacent wires, and angle of incidence of the light field with respect to the long wire axis. The dipolar peak shifts to larger wavelengths with increasing diameter and length, and diminishing mean distance between adjacent wires. Additionally, the shape effect on the dipolar peak is investigated.

On the propagation rate of the chemical waves observed during the course of CO oxidation on a Ag/Pt(110) composite surface

We have analyzed the propagation rate of the chemical waves observed during the course of CO oxidation on a Ag/Pt(I 10) composite surface that were reported in our previous papers [Surf Interface Anal. 2001, 32, 179; J. Phys. Chem. B 2002, 106, 5645]. In all cases, the propagation rate v can be adequately fitted as v = v(0) + D-0/d, in which v(0) and D-0 are constants, and d is the distance between the reaction front of the chemical wave and the boundary from which the chemical wave originates. We propose that the surface species responsible for the formation of the chemical wave comes from two paths: the adsorption of molecules in the gas phase on the surface and the migration from the adjacent surface with different catalytic activity. v(0) corresponds to the contribution from the surface species due to the adsorption, and D-0/d to that of the surface species that migrates from the adjacent surface. The rate equation clearly suggests that the observed chemical wave results from the coupling between adjacent surfaces with different catalytic activities during the course of heterogeneous catalysis. These results, together with our previous reports, provide a good fundamental understanding of spillover, an important phenomenon in heterogeneous catalysis.