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Register a new userFluctuation driven height reduction of crosslinked polymer brushes
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We study the changes in the conformations of brushes upon the addition of crosslinks between the chains using the bond fluctuation model. The Flory-Rehner model applied to uni-axially swollen networks predicts a collapse for large degrees of crosslinking $q$ proportional to $q^{-1/3}$ in disagreement with our simulation data. We show that the height reduction of the brushes is driven by monomer fluctuations in direction perpendicular to the grafting plane and not due to network elasticity. We observe that the impact of crosslinking is different for reactions between monomers of the same or on different chains. If the length reduction of the effective chain length due to both types of reactions is accounted for in a function $beta(q)$, the height of the brush can be derived from a Flory approach for the equilibrium brush height leading to $H(q)approx H_{b}beta(q)^{1/3}$, whereby $H_{b}$ denotes the height of the non-crosslinked brush.
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The organization of nano-particles inside grafted polymer layers is governed by the interplay of polymer-induced entropic interactions and the action of externally applied fields. Earlier work had shown that strong external forces can drive the formation of colloidal structures in polymer brushes. Here we show that external fields are not essential to obtain such colloidal patterns: we report Monte Carlo and Molecular dynamics simulations that demonstrate that ordered structures can be achieved by compressing a `sandwich of two grafted polymer layers, or by squeezing a coated nanotube, with nano-particles in between. We show that the pattern formation can be efficiently controlled by the applied pressure, while the characteristic length--scale, i.e. the typical width of the patterns, is sensitive to the length of the polymers. Based on the results of the simulations, we derive an approximate equation of state for nano-sandwiches.
A comparative simulation study of polymer brushes formed by grafting at a planar surface either flexible linear polymers (chain length $N_L$) or (non-catenated) ring polymers (chain length $N_R=2 N_L$) is presented. Two distinct off-lattice models are studied, one by Monte Carlo methods, the other by Molecular Dynamics, using a fast implementation on graphics processing units (GPUs). It is shown that the monomer density profiles $rho(z)$ in the $z$-direction perpendicular to the surface for rings and linear chains are practically identical, $rho_R(2 N_L, z)=rho_L(N_L, z)$. The same applies to the pressure, exerted on a piston at hight z, as well. While the gyration radii components of rings and chains in $z$-direction coincide, too, and increase linearly with $N_L$, the transverse components differ, even with respect to their scaling properties: $R_{gxy}^{(L)} propto N_L^{1/2}$, $R_{gxy}^{(R)} propto N_L^{0.4}$. These properties are interpreted in terms of the statistical properties known for ring polymers in dense melts.
We consider a polymer brush grafted to a surface (acting as an electrode) and bearing a charged group at its free end. Using a second distant electrode, the brush is subject to a constant electric field. Based on a coarse-grained continuum model, we calculate the average brush height and find that the brush can stretch or compress depending on the applied field and charge end-group. We further look at an undulation mode of the flat polymer brush and find that the electrostatic energy scales linearly with the undulation wavenumber, $q$. Competition with surface tension, scaling as $q^2$, tends to stabilize a lateral $q$-mode of the polymer brush with a well-defined wavelength. This wavelength depends on the brush height, surface separation, and several system parameters.
We present a method to generate realistic, three-dimensional networks of crosslinked semiflexible polymers. The free energy of these networks is obtained from the force-extension characteristics of the individual polymers and their persistent directionality through the crosslinks. A Monte Carlo scheme is employed to obtain isotropic, homogeneous networks that minimize the free energy, and for which all of the relevant parameters can be varied: the persistence length, the contour length as well as the crosslinking length may be chosen at will. We also provide an initial survey of the mechanical properties of our networks subjected to shear strains, showing them to display the expected non-linear stiffening behavior. Also, a key role for non-affinity and its relation to order in the network is uncovered.
Reversible crosslinking is a design paradigm for polymeric materials, wherein they are microscopically reinforced with chemical species that form transient crosslinks between the polymer chains. Besides the potential for self-healing, recent experimental work suggests that freely diffusing reversible crosslinks in polymer networks, such as gels, can enhance the toughness of the material without substantial change in elasticity. This presents the opportunity for making highly elastic materials that can be strained to a large extent before rupturing. Here, we employ Gaussian chain theory, molecular simulation, and polymer self-consistent field theory for networks to construct an equilibrium picture for how reversible crosslinks can toughen a polymer network without affecting its linear elasticity. Maximisation of polymer entropy drives the reversible crosslinks to bind preferentially near the permanent crosslinks in the network, leading to local molecular reinforcement without significant alteration of the network topology. In equilibrium conditions, permanent crosslinks share effectively the load with neighbouring reversible crosslinks, forming multi-functional crosslink points. The network is thereby globally toughened, while the linear elasticity is left largely unaltered. Practical guidelines are proposed to optimise this design in experiment, along with a discussion of key kinetic and timescale considerations.
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