Ultraslow Adsorption of Star <i>cis</i>-1,4-Polyisoprenes by In Situ Imbibition in Nanopores

Kardasis, Panagiotis; Sakellariou, Georgios; Floudas, George

doi:10.1021/acs.macromol.3c01760

Cited by 3 publications

(2 citation statements)

References 46 publications

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“…Within nanopores, the capillary force is strong and drives the lower viscosity compound (IL) to penetrate first. This is reminiscent of the component separation of blends composed of lower and higher molar mass polymers as well as the separation of blends of different polymer topologies , (e.g., topology sorting in linear/star polymer blends). Further studies will explore the limitations in the relative viscosity of the components required for the separation process.…”

Section: Resultsmentioning

confidence: 99%

“…Then we explored the way that mixtures of the PIL with the corresponding IL (based on the 1-butyl-3-methylimidazolium cation [BMIM] + , i.e., mixtures of poly[BVIM] + [X] − /[BMIM] + [X] − ) penetrate nanopores. Specifically, we investigate (i) the kinetics of imbibition, for the first time, using the newly established method of in situ nanodielectric spectroscopy, − ,, capable of measuring the ion dynamics during flow in nanopores, and (ii) the ion dynamics under confinement. We aim to address the following open questions: How do PIL/IL mixtures penetrate nanopores?…”

Section: Introductionmentioning

confidence: 99%

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Demixing of Polymerized Ionic Liquid/Ionic Liquid Mixtures by Infiltration in Nanopores

Dong,

Steinhart,

Butt

et al. 2024

Macromolecules

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Ion transport through membrane nanopores is pertinent to several applications, including water desalination and energy harvesting. We synthesized a series of polymerized ionic liquids (PILs) based on the 1-butyl-3-vinylimidazolium cation ([BVIM]+ with three different anions ([X]−: [TFSI]−, [BF4]−, [PF6]−). We explored how mixtures of the PIL with the corresponding IL (poly[BVIM]+[X]−/[BMIM]+[X]−) penetrate the nanopores. For this purpose, we employ ex situ reflection optical microscopy of the evolution of the imbibition length and in situ conductivity measurements by nanodielectric spectroscopy. The latter provides details of ion motion during and following imbibition. In the bulk, symmetric poly[BVIM]+[X]−/[BMIM]+[X]− mixtures are locally heterogeneous, composed of nearly pure IL domains and mixed PIL/IL domains. When the mixture is placed on top self-ordered nanoporous aluminum oxide templates (AAO), the ionic liquid is dragged by capillary action into the pores. During imbibition the two components partially demix. At the end of the filling process the pores contain an excess of the IL and a minority of PIL chains. Subsequently we explored the effect of polymer adsorption and surface functionality on the kinetics of ion transport. The results suggest the possibility to separate a mixture of ionic compounds (IL and PIL in this case) by the difference in the imbibition kinetics of its constituent components. Applications of AAOs as separation membranes for ionic systems are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Demixing of Polymerized Ionic Liquid/Ionic Liquid Mixtures by Infiltration in Nanopores

Dong,

Steinhart,

Butt

et al. 2024

Macromolecules

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View full text Add to dashboard Cite

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Capillary filling of star polymer melts in nanopores

Zhang,

Lei,

Feng

et al. 2024

The Journal of Chemical Physics

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The topology of a polymer profoundly influences its behavior. However, its effect on imbibition dynamics remains poorly understood. In the present work, capillary filling (during imbibition and following full imbibition) of star polymer melts was investigated by molecular dynamics simulations with a coarse-grained model. The reversal of imbibition dynamics observed for linear-chain systems was also present for star polymers. Star polymers with short arms penetrate slower than the prediction of the Lucas–Washburn equation, while systems with long arms penetrate faster. The radius of gyration increases during confined flow, indicating the orientation and disentanglement of arms. In addition, the higher the functionality of the star polymer, the more entanglement points are retained. Besides, a stiff region near the core segments of the stars is observed, which increases in size with functionality. The proportion of different configurations of the arms (e.g., loops, trains, tails) changes dramatically with the arm length and degree of confinement but is only influenced by the functionality when the arms are short. Following full imbibition, the different decay rates of the self-correlation function of the core-to-end vector illustrate that arms take a longer time to reach the equilibrium state as the functionality, arm length, and degree of confinement increase, in agreement with recent experimental findings. Furthermore, the star topology induces a stronger effect of adsorption and friction, which becomes more pronounced with increasing functionality.

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Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores

Kardasis,

Tzourtzouklis,

Nega

et al. 2024

The Journal of Chemical Physics

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We report the imbibition and adsorption kinetics of a series of symmetric linear/star cis-1,4-polyisoprene blends within the long channels of self-ordered nanoporous anodic aluminum oxide (abbreviated: AAO). Using in situ nanodielectric spectroscopy, we followed the evolution of the longest chain modes in the blends with a judicious selection of molar masses for the constituent components. We demonstrated differences in the imbibition kinetics of linear and star components based on the relative viscosities (e.g., polymers with lower zero-shear viscosity penetrated first the nanopores). Following the complete imbibition of the pores, the adsorption time, τads, of each component was evaluated from the reduction in the dielectric strength of the respective chain modes. In the majority of blends, both components exhibited slower adsorption kinetics with respect to the homopolymers. The only exception was the case of entangled stars mixed with shorter linear chains, the latter acting as a diluent for the star component. This gives rise to what is known as topology sorting, e.g., the separation of linear/star blend components in the absence of solvent. Moreover, a simple relation (τads ∼ 10 × tpeak; tpeak is the time needed for the complete filling of pores) was found for linear polymers and stars. This suggested that the characteristic timescale of imbibition (tpeak) governs the adsorption process of polymers. It further implied the possibility of predicting the adsorption times of high molar mass polymers of various architectures by the shorter imbibition times.

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Ultraslow Adsorption of Star cis-1,4-Polyisoprenes by In Situ Imbibition in Nanopores

Cited by 3 publications

References 46 publications

Demixing of Polymerized Ionic Liquid/Ionic Liquid Mixtures by Infiltration in Nanopores

Demixing of Polymerized Ionic Liquid/Ionic Liquid Mixtures by Infiltration in Nanopores

Capillary filling of star polymer melts in nanopores

Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores

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