Dynamic probe of the interface in lamellar forming non-linear block copolymers of the (BA) 3 B and (BA) 3 B(AB) 3 type. A dielectric spectroscopy study

Abstract Dielectric spectroscopy is employed in lamellar forming non-linear block copolymers of the type (BA) 3 B and (BA) 3 B(AB) 3 based on polyisoprene (A) and polystyrene (B), at temperatures well below the order-to-disorder transition temperature and below the glass transition temperature of the hard phase (polystyrene). We show here that dielectric spectroscopy can be used as a tool to probe the interface in ordered block copolymers with a basic triblock unit. Our estimate of the interfacial width is based on the mobility of the junction points at the interface and compares favorably with the estimated thickness from thermodynamics.

Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes

The synthesis, molecular and morphological characterization of a 3-miktoarm star terpolymer of polystyrene (PS, M¯¯¯¯n = 61.0 kg/mol), polybutadiene (PB, M¯¯¯¯n = 38.2 kg/mol) and polyisoprene (PI, M¯¯¯¯n = 29.2 kg/mol), corresponding to volume fractions (φ) of 0.46, 0.31 and 0.23 respectively, was studied. The major difference of the present material from previous ABC miktoarm stars (which is a star architecture bearing three different segments, all connected to a single junction point) with the same block components is the high 3,4-microstructure (55%) of the PI chains. The interaction parameter and the degree of polymerization of the two polydienes is sufficiently positive to create a three-phase microdomain structure as evidenced by differential scanning calorimetry and transmission electron microscopy (TEM). These results in combination with small-angle X-ray scattering (SAXS) and birefringence experiments suggest a cubic tricontinuous network structure, based on the I4132 space group never reported previously for such an architecture

Model block copolymers with complex architecture

The synthesis of non linear block copolymers of the type (BA)2B (3-miktoarm star copolymer), (BA)3B (4-miktoarm star copolymer), (BA)3B(AB)3 (super H-shaped), B2AB2 (H-shaped) and (B,A)A(B,A) (π-shaped), where A is polyisoprene 1,4 and B is polystyrene was performed using anionic polymerization techniques and suitable chlorosilane chemistry. Characterization data showed that the samples are molecularly and compositionally homogeneous. TEM, SAXS and SANS were used to study the microphase behavior of the copolymers. For all samples, the results were analyzed in the frame of the theoretical predictions given by Milner and taking into account the results from previous studies on the A2B and A3B miktoarm star copolymers

Hydrodynamic properties of A8B8 type miktoarm (Vergina) stars

The dilute solution properties of three (PS)8(PI)8 miktoarm (Vergina) stars were investigated by viscometry and dynamic light scattering in toluene and tetrahydrofuran (THF) (common good solvents), cyclohexane at 34.5 °C (theta solvent for PS and good for PI) and dioxane at 34 °C (theta solvent for PI and good for PS). Experimental intrinsic viscosity [η] and hydrodynamic radii, Rh, values in all solvents were larger for the miktoarm stars in comparison to the calculated ones using a simple model which describes the size of the copolymers as a weighted average of the sizes of the homopolymer stars with the same total molecular weight and number of arms as the copolymer. This expansion is discussed on the basis of the increased number of hetero-contacts, the topological constrains imposed by the common junction point in this highly branched miktoarm architecture and the asymmetry in molecular weights of the different kinds of arms. The conformation adopted in dilute solutions can explain, to some extent, the morphological results obtained on the same materials. The ratios of viscometric to hydrodynamic radii are consistent with previous investigations on linear and star polymers and in accord with the hard sphere model

Swelling behavior of ordered miktoarm star block copolymer-homopolymer blends

We report the morphological characterization of asymmetric miktoarm star block copolymers of the (PS-b-PI)n, PS type where n = 2, 3 (denoted 2DB and 3DB miktoarm stars, respectively) and a symmetric super H-shaped block copolymer of the (PS-b- PI)3PS(PI-b-PS)3 type (denoted SH) which were synthesized by anionic polymerization. The initial volume fraction of PS (φPS) for each copolymer was 0.51-0.56, giving a lamellar morphology. Addition of homopolystyrene (hPS) with a molecular weight lower than the respective PS blocks in the neat materials lead to a transition from the lamellar structure to hexagonally packed cylinders. Addition of low molecular weight homopolyisoprene (hPI) on the other hand, only resulted in swollen lamellae even when the overall composition was highly asymmetric (80/20). Changes in the lamellar spacing as well as in the respective PS and PI layer thickness were measured by SAXS. The transition from lamellae to cylinders with increased PS content occurred without the observation of an intervening cubic morphology for the 2DB and 3DB miktoarm stars. However, blends with 30 and 35% hPS (φPS)total = 0.68-0.70) with the super H-shaped block copolymer lead to the observation of lamellar-catenoid structures. © 2002 Elsevier Science Ltd. All rights reserved

Dynamic probe of the interface in lamellar forming non-linear block copolymers of the (BA)3B and (BA)3B(AB)3 type. A dielectric spectroscopy study

Dielectric spectroscopy is employed in lamellar forming non-linear block copolymers of the type (BA)3B and (BA)3B(AB)3 based on polyisoprene (A) and polystyrene (B), at temperatures well below the order-to-disorder transition temperature and below the glass transition temperature of the hard phase (polystyrene). We show here that dielectric spectroscopy can be used as a tool to probe the interface in ordered block copolymers with a basic triblock unit. Our estimate of the interfacial width is based on the mobility of the junction points at the interface and compares favorably with the estimated thickness from thermodynamics. © 1998 Elsevier Science B.V. All rights reserved