Polyhedral oligomeric silsesquioxane amphiphiles: isotherm and brewster angle microscopy studies of trisilanolisobutyl-POSS at the air/water interface. 
A trisilanol derivative of polyhedral oligomeric silsesquioxanes (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface.  Moreover, the trisilanolisobutyl-POSS monolayer undergoes a nonequilibrium structural transition (collapse) around a surface pressure of Rho approximately 18 mN.m(-1).  This paper explores the mono- and multilayer properties of POSS molecules at the air/water interface by the Wilhelmy plate technique and Brewster angle microscopy.  Surface concentrations are controlled by four mechanisms: (1) compression at a constant rate, (2) stepwise compression followed by surface pressure relaxation to an "equilibrium" value, (3) successive additions of spreading solution followed by relaxation to a stable surface pressure value, and (4) hysteresis loops to test the reversibility of the structural transitions.  Results show that both an increasing compression rate and a decreasing temperature lead to an increase in the surface pressure of the structural transition, which is consistent with the formation of solidlike multilayer domains during the collapse process.  For the case of compression at a constant rate, small domains initially form and later aggregate to form large solid masses.  Cessation of compression allows these large solid masses to relax into equilibrium ringlike structures with a lower surface pressure, Rho approximately 13 mN.m(-1).  In contrast, if the film is expanded rapidly, these large solidlike domains relax into "spaghetti" like networks with a residual surface pressure that depends on the initial amount of the solidlike collapsed phase.  Finally, successive addition and stepwise compression isotherm experiments lead to different and time-dependent morphologies.  Understanding these surface properties of POSS molecules affords an excellent opportunity to design and study POSS/polymer blends for coating applications where POSS molecules with rigid inorganic cores, soft organic coronae, and dimensions comparable to polymeric monolayers can serve as perfectly monodisperse nanofillers.