We perform lattice Monte Carlo simulation using the bond-fluctuation model to examine the conformation and dynamic properties of a single small flexible ring polymer in the matrix of linear chains as functions of the degree of polymerization of the linear chains. The average conformation properties as gauged by the mean-square radius of gyration and asphericity parameter are insensitive to the chain length for all the chain lengths examined ͑30, 100, 300, and 1000͒. However, in the longer chain ͑300 and 1000͒ samples, there is an increased spread in the distribution of the value of these quantities, suggesting structural heterogeneity. The center-of-mass diffusion of the ring shows a rapid decrease with increasing chain length followed by a more gradual change for the two longer chain systems. In these longer chain systems, a wide spread in the value of the apparent self-diffusion coefficient is also observed, as well as qualitatively different square displacement trajectories among the different samples, suggesting heterogeneity in the dynamics. A primitive path analysis reveals that in these long chain systems, the ring can exist in topologically distinct states with respect to threading by the linear chains. Threading by the linear chain can dramatically slow down and in some cases stall the diffusive motion of the ring. We argue that the life times for these topological conformers can be longer than the disentanglement time of the linear chain matrix, so that the ring exhibits nonergodic behavior on time scales less or comparable to the life time of these conformers. Our results suggest a picture of the ring diffusion as one where the diffusion path consists of distinctive segments, each corresponding to a different conformer, with slow interconversion between the different conformers.

No abstract

In this work, hydroxyl-functionalized boron nitride nanosheet (OH-BNNS) was prepared and was blended with poly(l-lactide) (PLLA) to yield PLLA/OH-BNNS nanocomposites with excellent dispersion of OH-BNNS via the interaction of carbonyl in PLLA and hydroxyl in OH-BNNS. The effects of OH-BNNS on the crystallization and melting behaviors, isothermal crystallization kinetics, macroscopic crystal morphology and crystal structure of PLLA were studied by means of various techniques. The addition of OH-BNNS nanofillers can effectively accelerate the crystallization of PLLA and enhance the nucleation density, leading to a smaller spherulite size, increased crystallinity, a more obvious crystallization peak upon cooling but weakened cold crystallization behavior upon heating. Low OH-BNNS loading can increase the relative content of α-crystal, but the relative content of less perfect α′-crystal is increased at high OH-BNNS loading due to the strong interaction between PLLA and OH-BNNS.

The influence of molecular topology on the structural and dynamic properties of polymer chain in solution with ring structure, three-arm branched structure, and linear structure are studied by molecular dynamics simulation. At the same degree of polymerization (N), the ring-shaped chain possesses the smallest size and largest diffusion coefficient. With increasing N, the difference of the radii of gyration between the three types of polymer chains increases, whereas the difference of the diffusion coefficients among them decreases. However, the influence of the molecular topology on the static and the dynamic scaling exponents is small. The static scaling exponents decrease slightly, and the dynamic scaling exponents increase slightly, when the topology of the polymer chain is changed from linear to ring-shaped or three-arm branched architecture. The dynamics of these three types of polymer chain in solution is Zimm-like according to the dynamic scaling exponents and the dynamic structure factors.

Polymer gel exists ubiquitously in our daily life, as in food, cosmetics, drugs, and so on. From the structural point of view, the 3D network can be found in a structural gel. In most experimental work, the gel is identified by the sharp increase in modules; that is, the gel should have similar properties as those of a solid, which is named as mechanical gel. However, not all structural gels have strong mechanical responses. Therefore, studying the relationship between structural gel and mechanical gel is very important. In this work, we investigate the structure and mechanical properties of symmetric ABA copolymers with solvophobic end blocks during the sol-gel transition. Three typical systems with weak, middle, and strong solvophobicities are simulated. It is found that the gelation concentration, gel structure, and mechanical response of structural gel are strongly affected by the solvophobicity of ABA block copolymer. We also find that only the gel formed in strong solvophobic systems has a strong mechanical response. Furthermore, the influence of solvophobicity of A-block on the static and dynamic properties of ABA block copolymers in solutions is also studied to give a molecular understanding of physical gelation.

Synthesis of covalent organic frameworks with long-range molecular orderings is an outstanding challenge due to the fact that defects against predesigned topological symmetries are prone to form and break crystallization....

Polymerization of monomers into two-dimensional covalent organic frameworks with precise porous structures exhibits desired catalytic, gas separation, and optoelectronic properties. However, the defects arising from covalent bonding in a polymerization process always result in amorphous films with small crystalline domains or polycrystalline powders. It is still a tremendous challenge to synthesize high-quality crystalline products, even single crystals with a large size over the micrometer scale. In this work, we propose a general strategy of building block design to reduce the defects during growth of two-dimensional covalent organic frameworks. We demonstrate that the building block with a hexagonal pore unit, i.e., a hexamer, could greatly decrease defects by directional uniform growth in polymerization, while monomer, dimer, and trimer building blocks form more defects due to linear growth. Our work provides a new strategy to construct superlarge single crystals in practical applications by combining building block design and growing dynamics control.

Poly (arylene ether)s can be designed to be amorphous, optically clear materials with excellent hydrolytic and thermal stability as well as good electrical, Mechanical and fire resistant properties. As a result, the use of these macromolecules in second order nonlinear optical (NLO) applications are being investigated. Typically, polymeric systems with doped chromophores result in a signigicant decrease in Tg. Methods were investigated to functionalize the polymer backbone with NLO chromophores, resulting in increased Tg.