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MMateartiearlisal2s022012,11,41,4x, 1F6O17R PEER REVIEW 10 of120of 20 gsrwoeulplisnginintbhoethcomveatlhenantoclraonssd-leitnhkasn.oAl smolountgionthseisdsimbliolcakr tomtehmatborafnPeAsN, w-batserdupprotatokne in- cerxecahsaendgwe mithemdbecrarenaesin[9g,2h2]y.dSruocphhiombpicr/ohvyedrsowpehlilliincgrcahtiaor.aTctheirsisitsicisnadriecaotnioenofotfhtehiencnhaatenges advantages of acrylic classes of polymers for PEM design. in water affinity which resulted in more severe membrane swelling. Fiigure 5. Uptakesoffdififeferernent ltiqliuqiudisdbsybtyhethcerocsrso-slisn-kliendkdedibldoicbkloiocnkoimoneormermmbreamnebsr.aAneNs.aAfioNn a11fi7on 1m17embermanberaisniencisluidnecdlufdoerdcofomrpcaormisopna.rison. Figures 6–8 show the swelling of the cross-linked diblock ionomer membranes and a In addition, the liquid uptake was also dependent on the type of alcohol solutions. Nafion 117 membrane in the in-plane (length and width) and through-plane (thickness) Specifically, methanol uptake was much lower than ethanol uptake. This is because rela- directions in water and pure alcohols (methanol and ethanol). The A50G4S-10 membrane tive to methanol, ethanol has a solubility parameter (δ) which is closer to the solubility shows the highest liquid uptake (Figure 5) and swelling among the three specimens, and parameters of most hydrocarbon monomer units (e.g., styrenic, acrylic, halide, and aro- is also greater in comparison with the other two diblock membranes. It is postulated that matic), and hence it can better solvate the hydrophobic segments. In addition, the reduced A50G4S-10, with the shortest hydrophobic block in an ordered polymer structure, induces Materials 2021, 14, x FOR PEER REVIEW 11 of 20 swelling of the cross-linked diblock membranes in alcohol solutions was expected, con- the formation of wider hydrophilic channels in the membrane and a high connectivity of sidering the poor solubility of acrylic polymers such as PAN (solubility parameter, δ = the hydrophilic domains. Consequently, a larger amount of water could be accommodated. 12.7) and MMA (δ = 9.5) in both methanol (δ = 7.4) and ethanol (δ = 9.5) [21]. Indeed, the extremely low swelling in both methanol and ethanol solutions is similar to that of PAN- based proton exchange membranes [9,22]. Such improved swelling characteristics are one of the innate advantages of acrylic classes of polymers for PEM design. Figures 6–8 show the swelling of the cross-linked diblock ionomer membranes and a Nafion 117 membrane in the in-plane (length and width) and through-plane (thickness) directions in water and pure alcohols (methanol and ethanol). The A50G4S-10 membrane shows the highest liquid uptake (Figure 5) and swelling among the three specimens, and is also greater in comparison with the other two diblock membranes. It is postulated that A50G4S-10, with the shortest hydrophobic block in an ordered polymer structure, induces the formation of wider hydrophilic channels in the membrane and a high connectivity of the hydrophilic domains. Consequently, a larger amount of water could be accommo- dated. FFiiggurree66..Dimimeennssioionnaallsstatabbiliiltiytyooffththeeccrroosss-l-ilninkkeeddddibiblolocckkioionnoomeerrmeembbraranneessininwaateter.r.ANaafifioonn 117 membrane is included for comparison. 117 membrane is included for comparison.PDF Image | Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer
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