Quantitative evaluation of evaporation rate during spin-coating of polymer blend films: Control of film structure through defined-atmosphere solvent-casting.

Thin films of polymer mixtures made by spin-coating can phase separate in two ways: by forming lateral domains, or by separating into distinct layers. The latter situation (self-stratification or vertical phase separation) could be advantageous in a number of practical applications, such as polymer optoelectronics. We demonstrate that, by controlling the evaporation rate during the spin-coating process, we can obtain either self-stratification or lateral phase separation in the same system, and we relate this to a previously hypothesised mechanism for phase separation during spin-coating in thin films, according to which a transient wetting layer breaks up due to a Marangoni-type instability driven by a concentration gradient of solvent within the drying film. Our results show that rapid evaporation leads to a laterally phase-separated structure, while reducing the evaporation rate suppresses the interfacial instability and leads to a self-stratified final film.

Responsive brushes and gels as components of soft nanotechnology.

Progress in the development of generic molecular devices based on responsive polymers is discussed. Characterisation of specially synthesised polyelectrolyte gels, "grafted from" brushes and triblock copolymers is reported. A Landolt pH-oscillator, based on bromate/ sulfite/ferrocyanide, with a room temperature period of 20 min and a range of 3.1 < pH < 7.0, has been used to drive periodic oscillations in volume in a pH responsive hydrogel. The gel is coupled to the reaction and changes volume by a factor of at least 6. A continuously stirred, constant volume, tank reactor was set-up on an optical microscope and the reaction pH and gel size monitored. The cyclic force generation of this system has been measured directly in a modified JKR experiment. The responsive nature of polyelectrolyte brushes, grown by surface initiated ATRP, have been characterised by scanning force microscopy, neutron reflectometry and single molecule force measurements. Triblock copolymers, based on hydrophobic end-blocks and either polyacid or polybase mid-block, have been used to produce polymer gels where the deformation of the molecules can be followed directly by SAXS and a correlation between molecular shape change and macroscopic deformation has been established. The three systems studied allow both the macroscopic and a molecular response to be investigated independently for the crosslinked gels and the brushes. The triblock copolymers demonstrate that the individual response of the polyelectrolyte molecules scale-up to give the macroscopic response of the system in an oscillating chemical reaction.

Neutron reflectivity studies of critical adsorption: the correspondence between a critical adsorption profile and specular neutron reflection.

For interfacial order parameter profiles which decay as Az(-mu), such as the composition profile of the noncritical interface of a binary liquid mixture at a critical end point, there is a reported one-to-one correspondence between the profile and the reflectivity which can be described by an analytical theory [S. Dietrich and R. Schack, Phys. Rev. Lett. 58, 140 (1987)]. Evidence for mu=0.53+/-0.02 for adsorption at the hydrophilic silicon/liquid surface of the mixture (2-butoxyethanol+deuterium oxide) near its lower critical end point, determined from neutron reflectivity measurements, is presented. This value is in good agreement with the theoretical prediction of mu=0.516+/-0.004. Further examination of the data permits the determination of the asymptotic surface enrichment scaling factor amplitude P0 approximately 0.11, which is not in agreement with the theoretical value P(0) = 0.94+/-0.05 and values determined by other experimental methods.