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Materials 2021, 14, 1617 Materials 2021, 14, x FOR PEER REVIEW m H2C CH + n H2C C CNOO CNOn 4 of 20 CH3 BPN CH3 CH C CH CuBr/bpy H C CH CH 65oCEC3 2 m 2 x3 4 of 20 HC CH3 O AN 2 CH H2C C O H2C H2C CH2 2 H2C O O CH2 H2C O GMA + y H3C CH2 CH CH2 C mnxy CNOO OO H2C H2C CH2 O Hydrophobic block CH2 OSO O K Hydrophilic block H2C H2C CH3 CH3 H2C OS O K SPM O CH2 C CH3 Figure 2. Synthesis of P[(AN-co-GMA)-b-SPM] diblock ionomer by the atom transfer radical poly- Figure 2. Synthesis of P[(AN-co-GMA)-b-SPM] diblock ionomer by the atom transfer radical mpeorliyzmateiorniz(aAtiToRnP()AteTcRhPn)iqtueceh. nique. 2.4. Characterizations 2.4. Characterizations 2.4.1. Electrochemical Analysis 2.4.1. Electrochemical Analysis The proton conductivities of the cast membranes were measured by the four-probe The proton conductivities of the cast membranes were measured by the four-probe measurement method on an Autolab PGSTAT30 (Metrohm Autolab B.V., Utrecht, Nether- lamnedass)uproetmenetniotsmtaett/hogdalvoannaonstAatuetqoulaipbpPeGdSwTiAthTa3n0e(lMecetrtorochemmAicualtoimlapbeBd.aVn.c,eUatnreaclyhzte,rN.eth- Tehrelafnrdeqs)upenocteynrtaionsgteato/fg1aMlvHanzotsota5t0eHquzipwpaesduwseidth. aAnllesleacmtrpolcehse(masi1caclmim×pe3dcamncsetrainpasl)yzer. wTehreferqeuqiuliebnracyterdaingdeeoiofn1iMzeHdzwtaote5r0foHrz2w4haspurisoerdt.oAthllesammeapsluesre(mase1ntcsm.T×he3mcmemstbrripans)ewere resistance was determined from the Nyquist plot of the complex impedance (Z” vs. Z’). equilibrated in deionized water for 24 h prior to the measurements. The membrane re- Proton conductivity was then calculated as σ = L , where L and S are the distance between sistancewasdeterminedfromtheNyquistplRoStofthecompleximpedance(Z”vs.Z’).Pro- 𝐿 the two electrodes (fixed at 1 cm) and the cross-sectional area of the membrane, respectively. ton conductivity was then calculated as 𝜎 = 𝑅𝑆, where L and S are the distance between The proton conductivity of a commercial Nafion 117 membrane measured this way was the two electrodes (fixed at 1 cm) and the cross-sectional area of the membrane, respec- between 0.05 and 0.07 S/cm. tively. The proton conductivity of a commercial Nafion 117 membrane measured this way 2w.4a.2s.bAeltcwoheoenlP0e.r0m5eaanbdil0it.y07atSR/comom. Temperature Ethanol permeability was measured at room temperature using a standard glass diffu- 2.4.2. Alcohol Permeability at Room Temperature sion cell. A membrane sample was first equilibrated in deionized water for 24 h. It was then mounted between the two compartments of a glass diffusion cell. One compartment Ethanol permeability was measured at room temperature using a standard glass dif- was filled with an ethanol solution of a known concentration (CA), and the other com- fusion cell. A membrane sample was first equilibrated in deionized water for 24 h. It was partment (the receiving compartment) was filled with ultra-pure water (CB). The 100-μL then mounted between the two compartments of a glass diffusion cell. One compartment samples were periodically drawn from the receiving compartment (every 40 min apart), was filled with an ethanol solution of a known concentration (CA), and the other com- and their compositions were analyzed by a Shimadzu GC-2010 (Shimadzu, Kyoto, Japan) partment (the receiving compartment) was filled with ultra-pure water (CB). The 100-μL gas chromatograph (GC) with a flame-ionization detector. The ethanol permeability was samples were periodically drawn from the receiving compartment (every 40 min apart), and their compositions were analyzed by a Shimadzu GC-2010 (Shimadzu, Kyoto, Japan) gas chromatograph (GC) with a flame-ionization detector. The ethanol permeability was calculated under pseudo steady-state conditions by the time dependence of using the for- mula shown below:PDF Image | Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer
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