Effective diameters for collisions of fractal-like aggregates: recommendations for improved aerosol coagulation frequency predictions

Fractal-like aggregate (FA-) drag has been previously calculated/correlated/reported, but "mobility diameter" information is not sufficient to make rational calculations of Brownian coagulation rates (for, say, population-balance modeling). Indeed, until now, only conjectures about gyration-radius scaling behavior have been used to predict FA-FA collision cross sections! But such "scaling relations" are untrustworthy even for FA momentum-, energy-, and mass-transfer purposes, and improved FA-collision rate constants (appearing as "kernels" in the coagulation balance integro-PDE) are overdue. Our premise is that FA collision rates in the free-molecule regime can be predicted using a gas-kinetic type formulation. If (a) carrier gas mean free path and FA persistence length are much larger than any characteristic FA size, (b) FA number density is low, (c) FA velocity and position are uncorrelated, and (d) there is a "hard-sphere" interaction between primary particles of different FAs, such a theory is developed/applied here. We introduce an effective collision diameter, , depending on the geometries of the two participating FAs. Quasi-MC calculations are reported for large ensembles of pairs of FAs, each computer-generated using a tunable cluster-cluster (CC)-algorithm. Our results differ from frequently used theoretical estimates based only on FA gyration (or mobility) radii and D(f). They also confirm that, if the size disparity of the colliding FAs is large, obtained by simply assigning individual diameters to each FA are significantly overestimated. Modified collision rate expressions for FA-coagulation modeling are suggested.     

Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.