The adsorption and desorption of functionalized
polystyrene-block-polybutadiene diblock
copolymers
from dilute solutions in toluene onto silicon wafers are investigated
by means of null ellipsometry. The
short polybutadiene block is functionalized by a reaction with
4-(3,5-dioxo-1,2,4-triazolidin-4-yl)benzoic
acid. On the average there are six functional groups per chain.
The polystyrene block does not adsorb
on the surface. The adsorption depends on the length of the
polystyrene block, and chains with short
polystyrene blocks yield higher surface coverage than larger ones.
When short and long chains are put
together, the short chains displace the long ones in equilibrium
conditions nearly completely. The desorption
seems to be partial if the bulk concentration of the short chains is
lower than a critical value, with the
likely formation of a heterogeneous layer composed of long and short
chains. At initial stages, adsorption
and desorption kinetics are both controlled by a diffusive process with
behavior. In the later
stages,
the desorption kinetics is roughly comparable to the adsorption
kinetics only in the systems where the
bulk concentration of the short chains is higher than a critical value.
At lower concentrations desorption
is slower than adsorption.
Polymer chain models on quadratic, cubic, triangular, and face-centered cubic lattices at volume fractions near unity are simulated with a Monte Carlo algorithm which transports beads from kinks or chain ends along the chain contour to another position of the chain by a slithering motion of the intervening chain part. Special cases are the slithering snake motion where the whole chain takes part in the slithering motion and a conformation change of a kink or an end group. For dense systems it is found that this algorithm is much more efficient than the slithering snake algorithm or algorithms which use only local motions. It can be used with good efficiency even for systems at a volume fraction of unity by moving chain parts collectively (collective motion algorithm). The computed chain dimensions agree with data obtained from other algorithms and with literature data.
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