Self-assembly of highly asymmetric, poly(ionic liquid)-rich diblock copolymers and the effects of simple structural modification on phase behaviour

Abstract

A series of ATRP-synthesized poly(IL) diblock copolymers exhibit morphological phase behavior with shifted phase boundaries and alkyl substituent dependent segregation.

Lithium-Ion Transport in Poly(ionic liquid) Diblock Copolymer Electrolytes: Impact of Salt Concentration and Cation and Anion Chemistry

“…In addition, the estimated peak assignments at q *, √4 q *, √7 q *, and √12 q * suggest a morphology of cylinders on a hexagonal lattice with PS as the cylindrical domains and concurs with the volume fractions listed in Table . A weakly ordered hexagonal-packed cylinder (HEX) morphology was also observed in the literature for PIL diblock copolymer with similar poly­(S- b -VBMIm + TFSI – ) compositions (i.e., conducting volume fraction, ϕ c = 0.79) . The average interdomain spacing, d *, can be directly calculated from the position of the primary scattering maximum, q *, with Bragg’s law: d * = 2π/ q * (listed in Table ).…”

“…A weakly ordered hexagonal-packed cylinder (HEX) morphology was also observed in the literature for PIL diblock copolymer with similar poly(S-b-VBMIm + TFSI − ) compositions (i.e., conducting volume fraction, ϕ c = 0.79). 52 The average interdomain spacing, d*, can be directly calculated from the position of the primary scattering maximum, q*, with Bragg's law: d* = 2π/q* (listed in Table 2). From Figure 5a and Table 2, all of the SPEs remain identical at the positions of the primary scattering peak, q*, with relatively constant domain spacings of ca.…”

A Perspective on the Design of Ion-Containing Polymers for Polymer Electrolyte Applications

“…Charged diblock copolymers are multicomponent polymeric systems usually consisting of a charged block and a neutral block, they possess unique self-assembly behaviors where ion transport provided by the charged block and mechanical support from the neutral block are combined. This unique behavior gives rise to their potential as solid polymer electrolytes in energy storage and conversion devices, among other aforementioned applications. − Phase behavior of charged block copolymers has been investigated actively over the last several years. − Ionic correlations introduced by the charged species drive phase segregation in ion-containing polymers, even in those systems whose neutral counterparts have no immiscibility at all, i.e., χN = 0 (where χ is the Flory–Huggins parameter that describes the compatibility between different types of monomers and N is the degree of polymerization). , In these cases, the skewed phase boundaries caused by phase segregation due to electrostatic effects (the “chimney effect”) results from the Coulombic interaction between charged monomers and counterions. The phase diagram also includes an inverted cylinder phase, where the majority component, i.e., the neutral block, forms the cylinders, whereas the charged block, which is the minority component of the charged diblock copolymers, forms the matrix.…”

Directional Self‐Assembly of Fluorinated Star Block Polymer Thin Films Using Mixed Solvent Vapor Annealing

“…The PFMA‐PS is not conformationally symmetric; however, the approximate volume fraction and asymmetry values of our polymers were close to f ~0.55 and b PMMA / b PS ~2 (see Table S1 for exact values). Thus, ( χN ) c values for the PFMA‐PS could be estimated as 11.5 for the linear PFMA‐PS and 9.0 for the three‐armed star PFMA‐PS on the basis of their conformational asymmetries and architectures, using phase diagrams available in the literature . The achievable lowest L 0 was obtained from ( χN ) c values (i.e., 10.5 for linear PMMA‐PS, 8 for star PMMA‐PS, 11.5 for linear PFMA‐PS, 9 for star PFMA‐PS) divided by the achievable N on the basis of calculated χ eff ‐ values for each polymer.…”