Open volume in bioadhesive detected by positron annihilation lifetime spectroscopy.

Barnacles attach to a wide variety of surfaces underwater and show substrate-specific adhesion mechanisms. Investigating and understanding these mechanisms is a key for developing new technical adhesives. We expected open volume (porosity) at the sub-nanometre scale to occur in barnacle adhesive. With positron annihilation lifetime spectroscopy (PALS) it is possible to detect porosity at the nanometre scale by determining the lifetime of positrons. This method has not been applied to bioadhesives so far. We showed that PALS is a suitable technique for the investigation of the barnacle base and its adhesive with respect to open volume. The results were interpreted using a standard model adapted from polymers. We thereby estimated pore sizes of 0.5 nm.

Temperature dependence of the free volume from positron lifetime experiments and its relation to structural dynamics: phenylphthalein-dimethylether.

Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of the free volume in the temperature range between 103 K and 393 K in phenylphthalein-dimethylether (PDE), a low-molecular-weight glass former. Using the routine LIFETIME9.0, the ortho-positronium (o-Ps) lifetime distribution was analyzed, and from this, the volume distribution gn(vh) of subnanometer-size holes was calculated. From a comparison of PALS and specific volume data, the number density and the volume fraction of holes were estimated. These free-volume data, as a function of temperature, were used to test the validity of the Cohen-Turnbull (CT) free-volume theory. It was found that the structural relaxation from dielectric spectroscopy can be described by the CT theory after introducing a corrected free volume (Vf-DeltaV), where DeltaV=0.014 cm3/g. The extended free-volume theory of Cohen and Grest can be fitted to the dielectric-relaxation and free-volume data, but the parameters of both fits are not consistent. PDE shows some peculiar features. The "knee" in the o -Ps lifetime expansion and crossover in temperature dependence of the frequency of the primary dielectric relaxation process occur at different temperatures. In addition, the change in the Vogel-Fulcher-Tammann parameters at TB/Tg=1.1 has no observable effect on the mean free volume vh (or Vf). The size of the smallest representative freely fluctuating subsystem, VSV estimated from the standard deviation sigmah of gn(vh), decreases from 4.1 nm3 to 2.6 nm3 when the temperature increases from T/Tg=1.0 to 1.15. Correspondingly, the length of dynamic heterogeneity, xi=VVS1/3, decreases from 1.6 nm to 1.4 nm. It is concluded that at T/Tg approximately 1.10=TB/Tg the system transforms from a heterogeneous to a homogeneous (true) liquid.