SANS Study of PPPO in Mixed Solvents and Impact on Polymer Nanoprecipitation

O’Connell, Róisín; Sharratt, William N.; Aelmans, Nico; Higgins, Julia S.; Cabral, João T.

doi:10.1021/acs.macromol.1c02030

Cited by 4 publications

(3 citation statements)

References 50 publications

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“…As the system consists of associative polymers, the SANS data were then fit to the correlation model, a highly intuitive approach that has been applied initially to understand the association of PEO in water. − This model was somewhat successful in the low sulfonation regime for dilute solutions. Though this model has been effective in fitting complex fluids that are locally segregated but homogeneous over larger length scales, − it did not capture the multiple length scales in our solutions.…”

Section: Methodsmentioning

confidence: 99%

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Kosgallana,

Senanayake,

Mohottalalage

et al. 2024

Macromolecules

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Ionic assemblies, or clusters, determine the structure and dynamics of ionizable polymers and enable their many applications. Fundamental to attaining well-defined materials is controlling the balance between the van der Waals interactions that govern the backbone behavior and the forces that drive the formation of ionic clusters. Here, using small-angle neutron scattering and fully atomistic molecular dynamics simulations, the structure of a model ionomer, sulfonated polystyrene in toluene solutions, was investigated as the cluster cohesion was tweaked by the addition of ethanol. The static structure factor was measured by both techniques and correlated with the size of the ionic clusters as the polymer concentration was varied. The conjunction of SANS results and molecular insight from MD simulations enabled the determination of the structure of these inhomogeneous networks on multiple length scales. We find that across the entire concentration range studied, a network driven by the formation of ionic clusters was formed, where the size of the clusters drives the inhomogeneity of these systems. Tweaking the ionic clusters through the addition of ethanol impacts the packing of the sulfonated groups, their shape, and their size distribution, which, in turn, affects the structure of these networks.

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Section: Methodsmentioning

confidence: 99%

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Kosgallana,

Senanayake,

Mohottalalage

et al. 2024

Macromolecules

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show abstract

“…Neutron scattering is a powerful technique that allows for the characterization of interfaces on the nanometer scale. It is widely used to characterize complex fluids such as microemulsions [11,12] and polymer solutions [13,14]. According to Wang and his co-workers, SANS can be used to extract quantitative, spatially resolved information about incipient soot formation and growth with better particle size resolution than light scattering and extinction [15].…”

Section: Small Angle Neutron Scattering (Sans)mentioning

confidence: 99%

A Review on Oil-Soluble Polyisobutylene-Based Dispersant for Colloidal Stabilization

Rahman,

Kei,

Ariffin

et al. 2023

MSF

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Oil soluble polymeric-based dispersants have been extensively used in engine oil lubrication formulation due to their inherent properties, such as modifiable viscosity, compatibility, and effectiveness. However, the underlying mechanism of how the dispersant stabilizes soot particles in engine oil is still not fully understood, and discovering this mechanism is crucial for engine oil formulation technology. This review discusses the interactions between colloidal particles induced by two PIBSA-derived dispersants, namely PIBSI and PIBSAE. The effectiveness of these dispersants in stabilizing colloidal particles in oil systems depends on the chemical functional groups present on the main chain. The spectrum of colloidal interactions, ranging from Derjaguin, Landau, Verwey and Overbeek (DLVO) to non-DLVO theory, is predominantly influenced by the equilibrium between dispersant concentration and the overall system viscosity. This phenomenon can eventually reverse colloidal stabilization and result in more serious issues, such as engine wear and tear.

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“…This mean-field approach allows for the interaction parameter (χ) at a specific concentration to be determined through small-angle X-ray scattering (SAXS) or small-angle neutron scattering (SANS), whereas light scattering is only able to obtain χ in dilute solutions. Previous studies have applied the RPA to determine χ for numerous polymer blends and solutions. − According to the mean-field approach, the Ornstein–Zernike equation can also be used to assess the correlation length (ξ), or the average distance between overlapping chain segments, beyond which chains no longer experience excluded volume effects from adjacent segments…”

Section: Introductionmentioning

confidence: 99%

Concentration and Temperature Dependence of the Interaction Parameter and Correlation Length for Poly(benzyl methacrylate) in Ionic Liquids

et al. 2022

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Polymers in ionic liquids (ILs) are a fascinating class of materials that exhibit unusual behavior in comparison to more traditional polymer solutions. Previous work characterizing the lower critical solution temperature (LCST) phase behavior of poly(benzyl methacrylate) (PBnMA)/IL mixtures demonstrated that the second virial coefficient is consistently positive, even at temperatures above the observed phase separation boundary, and that the critical composition is shifted strongly toward polymerrich compositions. To better understand these phenomena, smallangle X-ray scattering was utilized along with Ornstein−Zernike analysis to determine the interaction parameter and correlation length of PBnMA in four ILs (one pyrrolidinium-based and three imidazolium-based) as a function of temperature (25−170 °C), concentration (5−30 wt%), and molecular weight (32−76 kDa). The interaction parameter was shown to increase with polymer volume fraction, contrary to the concentration-independent behavior anticipated by Flory-Huggins theory, which clarified the unusual phase diagram of these solutions. The semidilute correlation length of PBnMA in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was shown to obey a temperature-concentration master curve; however, no such universal behavior was exhibited among the four ILs. Additionally, the concentration dependence of the correlation length was shown to decrease as the solvent quality worsened.

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SANS Study of PPPO in Mixed Solvents and Impact on Polymer Nanoprecipitation

Cited by 4 publications

References 50 publications

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

A Review on Oil-Soluble Polyisobutylene-Based Dispersant for Colloidal Stabilization

Concentration and Temperature Dependence of the Interaction Parameter and Correlation Length for Poly(benzyl methacrylate) in Ionic Liquids

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