Critical adsorption of copolymer tethered on selective surfaces.

Critical adsorption behaviors of flexible copolymer chains tethered to a flat homogeneous surface are studied by using Monte Carlo simulations. We have compared the critical adsorption temperature Tc, estimated by a finite-size scaling method, for different AB copolymer sequences with A the attractive monomer and B the inert monomer. We find that Tc increases with an increase in the fraction of monomers A, fA, in copolymers, and it increases with an increase in the length of block A for the same fA. In particular, Tc of copolymer (AnBn)r can be expressed as a function of the block length, n, and Tc of copolymer (AnB)r and (ABm)r can be expressed as a linear function of fA. Tc of random copolymer chains also can be expressed as a linear function of fA and it can be estimated by using weight-average of Tc of different diblocks in the random copolymer. However, the crossover exponent is roughly independent of AB sequence distributions either for block copolymers or for random copolymers.

Critical adsorption of a flexible polymer on a stripe-patterned surface.

The adsorption and dynamics of a polymer chain on a stripe-patterned surface composed of periodical attractive and neutral stripes are studied by using Monte Carlo simulation. The critical adsorption temperature Tc and pattern-recognition temperature Tr are estimated from the desorption probability, surface contact number, and bridge number. A phase diagram presenting three polymer states, including a desorbed state above Tc, a multi-stripe adsorbed state at an intermediate temperature Tr < T < Tc, and a single-stripe adsorbed state below Tr, is provided for infinitely long chains. Normal diffusion is always observed for a polymer in the direction parallel to the stripe even at low temperature. But in the direction perpendicular to the stripe, the polymer can freely diffuse above Tc, whereas the polymer is confined to one attractive stripe below Tr. However, the adsorbed polymer can hop from one attractive stripe to another at the intermediate temperature Tr < T < Tc.

Dynamics of a polymer adsorbed to an attractive homogeneous flat surface.

The adsorption of a bond fluctuation self-avoiding walk polymer on an attractive homogeneous flat surface at temperature below the critical adsorption point is studied using dynamic Monte Carlo simulation. Results show that the apparent size Rg,xy(2) of the polymer parallel to the surface increases exponentially with time during the adsorption process. The relaxation time for Rg,xy(2) reaching its asymptotic value σeq decreases with the increase in the polymer-surface attraction strength Eps, whereas σeq increases with Eps, indicating that the polymer is adsorbed faster and becomes more extended at stronger adsorption. The polymer's asphericity Axy parallel to the surface is sensitive to intra-polymer interaction and its behavior is different from that of Rg,xy(2). Simulation results also show that the two-dimensional behaviors of Rg,xy(2) and Axy are different from that of the three-dimensional conformational size Rg(2) and asphericity A during the adsorption process. During the adsorption, the surface contacted monomer number M increases with time, but Rg(2) and A show novel behavior as they first increase with M at small M, then decrease with M at moderate M and finally increase with M again at large M. Whereas Rg,xy(2) and Axy first decrease with M and then increase with M during the adsorption.

Study on the polymer diffusion in a media with periodically distributed nano-sized fillers.

The effect of nano-sized fillers on the equilibrium and dynamical properties of a linear polymer is studied by using off-lattice Monte Carlo simulation. Fillers are arranged periodically in the system with period d and Lennard-Jones interaction between polymer and fillers is considered. Results show that the statistical dimension and dynamical diffusion of the polymer are dependent on the polymer-filler interaction strength ɛ(pf) and the relative size between R(G0) and d, here R(G0) is the radius of gyration of polymer in dilute solution. Normal diffusion of polymer is always observed in the regime 2R(G0) > d. And the diffusion coefficient D is scaled with chain length N as D ~ N(-α), where the exponent α increases with ɛ(pf). Whereas in the regime 2R(G0) < d ≪ Nl0 with l0 the mean bond length of polymer, normal diffusion is observed only at ɛ(pf) < 2, but the polymer will be adsorbed on the fillers and cannot diffuse at ɛ(pf) > 2. In addition, we find that there is a critical interaction strength ɛ*(pf) = 2 in our model system.

Critical adsorption of a flexible polymer confined between two parallel interacting surfaces.

Critical adsorption of a lattice self-avoiding bond fluctuation polymer chain confined between two parallel impenetrable surfaces is studied using the Monte Carlo method. The dependence of the mean contact number on the temperature T and on the chain length N is simulated for a polymer-surface interaction E=-1. A critical adsorption of the polymer is found at T(c)=1.65 for large surface separation distance D>N(ν)b, whereas no critical adsorption is observed for small distance D