PBTTT-C16 sol-gel transition by rod associations and networking.

A low-molecular-weight poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (designated as Lw-pBTTT-C16) in a fair solvent (chlorobenzene, CB) displays peculiar structural, mechanical, and electronic features during sol-gel transition. Using comprehensive (multiscale) dynamic/static analysis schemes, the Lw-pBTTT-C16/CB solution (10 mg mL-1) is shown to capitalize on rod associations and networking to form a gel, in stark contrast with its high-molecular-weight companion previously reported to form gels through hierarchical colloidal bridging. The present study reveals, however, that the molecular weight of pBTTT-C16 has a subtle impact on the gelation behaviors through the rarely recognized, contrasting supramolecular conformations (rod-like vs. wormlike) of the aggregate clusters fostered in the pristine solution. The ac conductivity nearly doubles as a result of improved (mesoscale) packing of cylindrical aggregates near the gel state as well as enhanced backbone rigidity of the constituting chains. Other distinguishing features include: (1) there is no real crossover of the dynamic moduli (G' and G'') upon increasing the temperature from gel (T = 15 °C) to solution (T = 80 °C) states. (2) The gel is about a hundredfold softer in dynamic modulus, yet more resilient with a fivefold increase in the yield strain. Both viscoelastic features are expected to greatly benefit the gel processability. (3) The coexistent microgels and cylinder (aggregate) bundles form a peculiar gel network that has not been reported previously with polymer or colloidal gels. The overall findings provide new mechanistic insight into the phenomenological effects of molecular weight for the pBTTT-Cn series in solution, sol, gel, and thin film.

Solution properties of imidazolium-based amphiphilic polyelectrolyte in pure- and mixed-solvent media.

The solution properties of a synthesized imidazolium-based amphiphilic polyelectrolyte dissolved in pure- and mixed-solvent media composed of two aprotic polar solvents (N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP)) having a similar dielectric constant are explored in the semidilute regime (1-4 wt%). Rheological characterizations reveal that the use of mixed-solvent media (e.g., DMAc/NMP with 1 : 1 in volume fraction, designated as 1 : 1 DMAc/NMP) leads to a substantial reduction in the solution viscosity while altering the fluid attribute from gel-like (G' > G'') to critical-gel-like (G' ∼ G'' ∼ ωn, with n ≅ 0.5). To gain insight into these peculiar rheological features, dynamic light scattering analysis of the representative 1 : 1 DMAc/NMP medium indicates that the fraction and mean hydrodynamic radius of the micrometer-sized cluster alter substantially, too. Multiscale static light/X-ray scattering characterizations further reveal that only the NMP and 1 : 1 DMAc/NMP media (and not the DMAc) are capable of producing hierarchical structures of the cluster interior that are beneficial to mesoscale ion conduction, as supported by ac conductivity measurements. Overall, the present findings suggest that an appropriate selection of mixed-solvent media may offer an exceptional opportunity to promote the rheological, structural, and ion-conduction properties of a polyelectrolyte solution beyond the reach of the corresponding pure-solvent media.

PBTTT-C16 sol-gel transition by hierarchical colloidal bridging.

A versatile conjugated polymer, poly(2,5-bis(3-hexadecyllthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT-C16, with Mw = 61 309 g mol-1), in a relatively good solvent (chlorobenzene, CB) medium is shown to produce gels through hierarchical colloidal bridging. Multiscale static/dynamic light and X-ray scattering analysis schemes along with complementary microscopy imaging techniques clearly reveal that upon cooling from the solution state at 80 °C to various gelation temperatures (5, 10, and 15 °C), rod-like colloidal pBTTT-C16 aggregates morph into spherical ones, triggering hierarchical colloid formation and bridging that eventually turn the solution into a gel after about one-day aging. A certain fraction of primal packing units-spherical gelators (∼1 nm in mean radius)-constitute the spherical building particles (∼10 nm) noted above, which in turn constitute loose-packing aggregate clusters (∼300 nm) in the sol state. As gelation proceeds, the aggregate cluster interiors tighten substantially, and micrometer-sized clusters (∼3 µm) formed by them begin to take shape and further interconnect to form the gel network (mean porosity size ∼240 nm and spatial inhomogeneity length ∼20 µm). Rheological measurements and kinetic analysis reveal that the gelation temperature can also have a notable impact on gel microstructure, gelation rate, and mechanical strength, resulting in, for instance, a prominently nonergodic and porous structure for the soft gel incubated at a higher temperature T = 15 °C. The ac conductivity exhibits a notable upturn near pBTTT-C16/CB gelation, well above those achieved by the counterpart pBTTT-C14 solutions, which, in interesting contrast, cannot be brought to the gel phase under similar experimental conditions.

Ethylcellulose Colloids Incubated in Dilute Solution.

This study revealed, for the first time, that dilute solutions made of a representative series of commercial ethylcellulose (EC; molecular weights 77-305 kDa, provided by the manufacturer) and four distinct organic solvents (α-terpineol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TPIB), tetrahydrofuran (THF), and benzene) can be used to foster stabilized, nearly monodisperse, nanoscale (pure) polymer colloid, with no isolated chains present. Using combined light-scattering (dynamic light scattering, static form factor, and Zimm/Berry plots) and intrinsic viscosity (Tanglertpaibul-Rao, Huggins, and Kraemer plots) analyses, the structural features of colloidal EC aggregates, ρ = ⟨Rg⟩/⟨Rh⟩ = 0.67-0.83, were first shown to be described rather well by the theory on colloidal spheres (⟨Rg⟩ and ⟨Rh⟩ being the mean radius of gyration and the hydrodynamic radius, respectively). An empirical scaling law relating the intrinsic viscosity to the mean colloid size can thus be established: [η]H = (1.7 ± 0.2) ×10-3 ⟨Rh⟩(2.1±0.3) ([η]H and ⟨Rh⟩ in units of mL/g and nm, respectively), which may be contrasted with the Zimm model for isolated Gaussian coils, [η]H ∼ ⟨Rh⟩1, and the Einstein equation for isolated solid spheres, [η]H ∼ ⟨Rh⟩0. Optical microscopy images of thin films cast from different EC solutions clearly revealed the abundance of micron EC agglomerates, contrary to the uniform thin-film morphology produced from a dilute polystyrene solution, which serves as a reference solution composed of isolated chains. These observations point to new features and applications of EC dispersions.