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addition, solvent-thermal post-treatment, organic-inorganic blending, and even film stretching. [1] Different compounds like polar solvents, salt, strong acids, ionic liquids, carbon nanotube, e.g., were utilized as additives, post-treatment agents, or blending components. For example, Saxena et al. post-treated pristine PEDOT:PSS films with various ionic liquids to induce an increased π-π stacking between PEDOT molecules. [4] 1-ethyl-3-methylimidazolium tetracyanoborate (EMIM TCB) treated films exhibited a record short π-π stacking distance of 3.35 Å due to an enormous bonding effect of TCB to PEDOT and EMIM to PSS and subsequent phase separation. Fan et al. reported an impressive electrical conductivity of 3088 S cm −1 after the exposure of PEDOT:PSS:5% DMSO (dimethyl sulfoxide) films with sulfuric acid. [3] Worfolk et al. reported solution sheared PEDOT:PSS films further posttreated with methanol with extremely high conductivity of 4600 S cm −1. [2] Among various strategies, polar solvents addition and post-treatment are among the most used and most efficient ways to improve PEDOT:PSS electrical conductivity. [1,5-8] Both processes can induce different effects on PEDOT:PSS thin films, such as π-π stacking distance shortening (i.e., increased π-π orbital overlap), alteration of the crystallite orientation (face-on vs edge-on), overall crystallinity increase, PSS removal, and phase separation. [9,10] Polar solvents with high dielectric constants and high boiling points are common additives and post-treatment agents, especially DMSO and EG (ethylene glycol). In 2002, Kim et al. reported for the first time about the use of DMSO as an additive to dramatically increased the conductivity of PEDOT:PSS thin films (about two orders of magnitude higher at room temperature), and since then polar solvents got more and more attention from the research field. [11,12] Pipe et al. reported a promising thermoelectric property for PEDOT:PSS by EG dip treatment following pre-doping PEDOT:PSS nanofilms with DMSO or EG. [13] The DMSO and EG pre-doped films exhibited σ > 600 S cm −1. After dipping them into an EG bath, conductivities up to 1000 S cm −1 were obtained, which were three orders of magnitude higher than pristine PEDOT:PSS. The effective improvement was mainly attributed to the selective removal of excessive PSS. Palumbiny et al. observed that the in-plane electrical conductivity of PEDOT:PSS increased from 0.2 to 1200 S cm −1 upon EG treatment. The authors drew the emphasis on the formation of larger PEDOT crystallites with more pronounced Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied conductive polymers, holding great potential in many applications such as thermoelectric generators, solar cells, and memristors. Great efforts have been invested in trying to improve its mechanical and electrical properties and to elucidate the structure-property relationship. In this work, a systematic and quantitative study of the effect of solvent polarity and solution processing on the f...
addition, solvent-thermal post-treatment, organic-inorganic blending, and even film stretching. [1] Different compounds like polar solvents, salt, strong acids, ionic liquids, carbon nanotube, e.g., were utilized as additives, post-treatment agents, or blending components. For example, Saxena et al. post-treated pristine PEDOT:PSS films with various ionic liquids to induce an increased π-π stacking between PEDOT molecules. [4] 1-ethyl-3-methylimidazolium tetracyanoborate (EMIM TCB) treated films exhibited a record short π-π stacking distance of 3.35 Å due to an enormous bonding effect of TCB to PEDOT and EMIM to PSS and subsequent phase separation. Fan et al. reported an impressive electrical conductivity of 3088 S cm −1 after the exposure of PEDOT:PSS:5% DMSO (dimethyl sulfoxide) films with sulfuric acid. [3] Worfolk et al. reported solution sheared PEDOT:PSS films further posttreated with methanol with extremely high conductivity of 4600 S cm −1. [2] Among various strategies, polar solvents addition and post-treatment are among the most used and most efficient ways to improve PEDOT:PSS electrical conductivity. [1,5-8] Both processes can induce different effects on PEDOT:PSS thin films, such as π-π stacking distance shortening (i.e., increased π-π orbital overlap), alteration of the crystallite orientation (face-on vs edge-on), overall crystallinity increase, PSS removal, and phase separation. [9,10] Polar solvents with high dielectric constants and high boiling points are common additives and post-treatment agents, especially DMSO and EG (ethylene glycol). In 2002, Kim et al. reported for the first time about the use of DMSO as an additive to dramatically increased the conductivity of PEDOT:PSS thin films (about two orders of magnitude higher at room temperature), and since then polar solvents got more and more attention from the research field. [11,12] Pipe et al. reported a promising thermoelectric property for PEDOT:PSS by EG dip treatment following pre-doping PEDOT:PSS nanofilms with DMSO or EG. [13] The DMSO and EG pre-doped films exhibited σ > 600 S cm −1. After dipping them into an EG bath, conductivities up to 1000 S cm −1 were obtained, which were three orders of magnitude higher than pristine PEDOT:PSS. The effective improvement was mainly attributed to the selective removal of excessive PSS. Palumbiny et al. observed that the in-plane electrical conductivity of PEDOT:PSS increased from 0.2 to 1200 S cm −1 upon EG treatment. The authors drew the emphasis on the formation of larger PEDOT crystallites with more pronounced Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied conductive polymers, holding great potential in many applications such as thermoelectric generators, solar cells, and memristors. Great efforts have been invested in trying to improve its mechanical and electrical properties and to elucidate the structure-property relationship. In this work, a systematic and quantitative study of the effect of solvent polarity and solution processing on the f...
From published HE data for 10 n‐alkane solutions in benzene at 25°C, the three parameters of the author's solution theory have been calculated. The values obtained agree quite well with εΔ = 3068 J/mole, K = 1, and rσ = 0.2 + 0.2 nc = 0.1 nH. The problems involved in the extension of these results to higher oligomers of polymethylene and to other solutions of chain molecules are briefly discussed.
An attempt is made to treat the formation of supercrystalline lattices in solution of melts of block copolymers on the macromolecular level using the effective flexibility parameters appearing in the equivalence principle of thermokinetics. All known data are in accord with the assumption which proposes an extremal dependence of the interaction of χ and χAB parameters on composition (χAB attaining its maximal value at A/B molar ratios close to unity). Therefore, the effective flexibility parameters fA and fB characterizing the corresponding blocks should pass through a minimum close to the χ maxima, the lines for fA and fB being, however, somewhat shifted along the composition axis. At first sight this type of behavior fits the experimental data, but closer consideration shows that the assumption of chain extension due to segreation inherently appearing in the whole concept does not hold. Therefore the situation is reconsidered, and it is shown that if the units (i.e., spheres, cylinders, and lamellae) occupying the sites of the superlattice are treated as “supermacromolecules” (or structons, following a somewhat improved definition of Huggins) the earlier theory holds. Moreover, it is shown that the supercrystals can be treated in terms of the kinetic theory of liquids and real crystals which leads to a understandable explanation of their unusual properties, especially their high thermal stability. Probably a general theory starting from ideal supercrystals may be developed by means of a stepwise introduction of paracrystalline defects (in the manner of Hosemann) in the lattice. The most disordered paracrystalline lattices will then correspond to polymer blends. Special attention is given to the formation of ordered structures from extended (or extruded) binary melts, the segregation parameter ϕAB being high, but where no junctions between A and B components occurs. This corresponds to the so‐called Yudin effect, and a catastrophic deliberation of the excess enthalpy of mixing on elimination of the noncrystallizable component (matrix) leads to an annihilation of the nematic units on annealing, thus showing the influence of the ϕAB parameter on the thermodynamic and morphologic properties of the structon forming component. Finally, something of the nature of ϕAB in phase equilibria during polymerization and its influence on the molecular‐weight distribution of branches during the course of graft copolymerization are considered.
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