Microphase Separation in Weakly Charged Annealed Gels and Associating Polyelectrolyte Solutions

2000 ◽  
Vol 33 (15) ◽  
pp. 5644-5654 ◽  
Author(s):  
Alexander N. Kudlay ◽  
Igor Ya. Erukhimovich ◽  
Alexei R. Khokhlov
Keyword(s):  
Microphase Separation ◽  
Polyelectrolyte Solutions

scholarly journals Two regions of microphase separation in ion-containing polymer solutions

Soft Matter ◽  
2017 ◽  
Vol 13 (38) ◽  
pp. 6831-6844 ◽  
Author(s):  
Artem M. Rumyantsev ◽  
Elena Yu. Kramarenko
Keyword(s):  
Polymer Solutions ◽  
Microphase Separation ◽  
Ion Association ◽  
New Type ◽  
Polyelectrolyte Solutions

A new type of microphase separation driven by ion association is theoretically predicted in concentrated polyelectrolyte solutions.

Microphase separation in poor-solvent polyelectrolyte solutions: Phase diagram

1994 ◽  
Vol 3 (4) ◽  
pp. 661-675 ◽  
Author(s):  
Elena E. Dormidontova ◽  
Igor Ya. Erukhimovich ◽  
Alexei R. Khokhlov
Keyword(s):  
Phase Diagram ◽  
Microphase Separation ◽  
Polyelectrolyte Solutions ◽  
Poor Solvent

Morphological studies of linear (AB)n multiblock copolymers and their blends

1992 ◽  
Vol 50 (1) ◽  
pp. 384-385
Author(s):  
Richard J. Spontak ◽  
Steven D. Smith ◽  
Arman Ashraf
Keyword(s):  
Electron Microscopy ◽  
Microphase Separation ◽  
Multiblock Copolymers ◽  
First Order ◽  
Morphological Studies ◽  
Transmission Electron ◽  
First Order Phase Transition ◽  
Covalently Bonded ◽  
Total Molecular Weight ◽  
First Order Phase

Block copolymers are composed of sequences of dissimilar chemical moieties covalently bonded together. If the block lengths of each component are sufficiently long and the blocks are thermodynamically incompatible, these materials are capable of undergoing microphase separation, a weak first-order phase transition which results in the formation of an ordered microstructural network. Most efforts designed to elucidate the phase and configurational behavior in these copolymers have focused on the simple AB and ABA designs. Few studies have thus far targeted the perfectly-alternating multiblock (AB)n architecture. In this work, two series of neat (AB)n copolymers have been synthesized from styrene and isoprene monomers at a composition of 50 wt% polystyrene (PS). In Set I, the total molecular weight is held constant while the number of AB block pairs (n) is increased from one to four (which results in shorter blocks). Set II consists of materials in which the block lengths are held constant and n is varied again from one to four (which results in longer chains). Transmission electron microscopy (TEM) has been employed here to investigate the morphologies and phase behavior of these materials and their blends.

Donnan Equilibria in Polymeric Micellar Systems with Weak Polyelectrolyte Shells: The Lowering of the pH Value

1997 ◽  
Vol 62 (11) ◽  
pp. 1730-1736 ◽  
Author(s):  
Petr Munk ◽  
Zdeněk Tuzar ◽  
Karel Procházka
Keyword(s):  
Ionic Strength ◽  
Block Copolymer ◽  
Ph Value ◽  
Electrolyte Solutions ◽  
Hydrogen Ions ◽  
Micellar Systems ◽  
Weak Electrolytes ◽  
Block Copolymer Micelles ◽  
Copolymer Micelles ◽  
Polyelectrolyte Solutions

When two electrolyte solutions are separated and only some of the ions can cross the boundary, the concentrations of these ions are different on both sides of the boundary. This is the well-known Donnan effect. When weak electrolytes are involved, the imbalance includes also hydrogen ions: there is a difference of pH across the boundary and the dissociation of nondiffusible weak electrolytes is suppressed. The effect is very pronounced when the concentration of the weak electrolyte is high and ionic strength is low. The significance of this phenomenon is discussed for polyelectrolyte solutions, and particularly for block copolymer micelles with weak polyelectrolyte shells. The effect is quite dramatic in the latter case.

scholarly journals Bottlebrush polymers in the melt and polyelectrolytes in solution share common structural features

2020 ◽  
Vol 117 (10) ◽  
pp. 5168-5175 ◽  
Author(s):  
Joel M. Sarapas ◽  
Tyler B. Martin ◽  
Alexandros Chremos ◽  
Jack F. Douglas ◽  
Kathryn L. Beers
Keyword(s):  
Neutron Scattering ◽  
Correlation Length ◽  
Salt Concentration ◽  
Polymer Concentration ◽  
Structural Features ◽  
Peak Position ◽  
Correlation Peak ◽  
Grafting Density ◽  
Scattering Measurements ◽  
Polyelectrolyte Solutions

Uncharged bottlebrush polymer melts and highly charged polyelectrolytes in solution exhibit correlation peaks in scattering measurements and simulations. Given the striking superficial similarities of these scattering features, there may be a deeper structural interrelationship in these chemically different classes of materials. Correspondingly, we constructed a library of isotopically labeled bottlebrush molecules and measured the bottlebrush correlation peak position q*=2π/ξ by neutron scattering and in simulations. We find that the correlation length scales with the backbone concentration, ξ∼cBB−0.47, in striking accord with the scaling of ξ with polymer concentration cP in semidilute polyelectrolyte solutions (ξ∼cP−1/2). The bottlebrush correlation peak broadens with decreasing grafting density, similar to increasing salt concentration in polyelectrolyte solutions. ξ also scales with sidechain length to a power in the range of 0.35–0.44, suggesting that the sidechains are relatively collapsed in comparison to the bristlelike configurations often imagined for bottlebrush polymers.

scholarly journals Quadruple Hydrogen Bond-Containing A-AB-A Triblock Copolymers: Probing the Influence of Hydrogen Bonding in the Central Block

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4705
Author(s):  
Boer Liu ◽  
Xi Chen ◽  
Glenn A. Spiering ◽  
Robert B. Moore ◽  
Timothy E. Long
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Microphase Separation ◽  
Triblock Copolymers ◽  
Random Copolymer ◽  
Thermomechanical Properties ◽  
Structure Property ◽  
Scanning Calorimetry ◽  
Central Block ◽  
Quadruple Hydrogen Bonding

This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan delta (δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.

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