Thermally Induced Microstructure Transitions in a Block Copolymer Ionomer

Lu, Xinya; Steckle, Warren P.; Hsiao, Ben; Weiß, Robert

doi:10.1021/ma00112a031

Cited by 26 publications

(30 citation statements)

References 13 publications

(16 reference statements)

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“…21,22 However, the development of novel materials offering higher proton conductivity requires fundamental understanding of micro-phase separation in the presence of charges, and this needs to be more thoroughly developed. Optimization of the proton transporting channels resulting from micro-phase separation and optimizing the mechanical properties of the materials are some of the directions 5,8,[23][24][25][26] that need to be pursued in order to achieve this goal. The early morphological knowledge in this area was mainly extracted from studying physical properties of ionized multiblock thermoplastic elastomers.…”

Section: Monojoy Goswamimentioning

confidence: 99%

Morphologies of block copolymers composed of charged and neutral blocks

et al. 2012

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This article reviews current experimental observations and theoretical calculations devoted towards understanding micro-phase separation in charged block copolymer systems. We discuss bulk morphologies in melt and in solution, as well as some of the new emerging research directions. Overall, a comprehensive picture is beginning to emerge on the fundamental role of electrostatics in the microphase separation of charged block copolymers. This understanding provides exciting new insight that may be used to direct targeted structures that endow the materials with desired properties that can have tremendous potential in technological applications.

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Section: Monojoy Goswamimentioning

confidence: 99%

Morphologies of block copolymers composed of charged and neutral blocks

et al. 2012

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“…Several reports on the morphology and physical properties of proton conducting membranes based on the polystyrene-containing block copolymers have been published. These include partially sulfonated poly(styrene-b-[ethylene-co-butylene]-b-styrene) (S-SEBS), [8][9][10][11][12][13][14][15][16] sulfonated poly(styrene-b-isobutylene-b-styrene) (S-SIBS), [17][18][19][20][21] sulfonated hydrogenated poly(butadiene-b-styrene) (S-HPBS), 22,23 sulfonated poly-(styrene-b-ethylene-alt-propylene) (S-SEP), 24,25 and poly-(styrene-b-ethylene/propylene-b-styrene) (S-SEPS) copolymer. 24 In related block copolymer studies, graft copolymers of PS-g-macPSSA show enhanced conductivity compared to that of random copolymers of styrene and styrenesulfonic acid (PS-r-PSSA).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Proton Conductivity of Partially Sulfonated Poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) Block Copolymers

2005

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=aeb1ea6c-9c47-4565-9a16-283705ab0182 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=aeb1ea6c-9c47-4565-9a16-283705ab0182 Synthesis and Proton Conductivity of Partially Sulfonated Poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) Block CopolymersZhiqing Shi and Steven Holdcroft* Department of Chemistry, Simon Fraser University, Burnaby, BC V5A 1S6, Canada, and Institute for Fuel Cell Innovation, National Research Council (NRC), 3250 East Mall, Vancouver, BC V6T 1W5, Canada Received November 2, 2004; Revised Manuscript Received February 18, 2005 ABSTRACT: A series of novel, amphiphilic block copolymers comprising of sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) [P(VDF-co-HFP)-b-SPS] were synthesized. The numberaverage molecular weights of the fluorous and polystyrene segments were 17 900 and 8100 g/mol, respectively. Sulfonation of the polystyrene segment to different extents provided a series of polymers which were cast into films to yield proton exchange membranes with varying ion exchange capacity (IEC). Proton conductivity of the membranes increased significantly when the IEC was increased from 0.5 to 1.2 mmol/g. For 0.9-1.2 mmol/g IEC membranes, the conductivity was similar to Nafion 117, significantly higher than random copolymers of polystyrene and sulfonated polystyrene, and twice that of nonfluorous block copolymer membranes based on sulfonated poly(styrene-b-[ethylene-co-butylene]-b-styrene) (S-SEBS) and sulfonated hydrogenated poly(butadiene-b-styrene) (S-HPBS) copolymers. TEM revealed a disruption in ordered morphology with increasing degree of sulfonation. Morphological structures of membranes having 0.6-1.2 mmol/g IEC comprised of interconnected networks of ion channels, each of 8-15 nm width.

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“…In our experiment, the q value associated with ionic aggregation was larger than q values mentioned in previous reports. This is because the higher sulfonation level of 30 % cesium salts causes smaller d-spacing compared with previous reports [5,26,29] . From Eq.…”

Section: Ps-b-poly(butadiene)-ps Block Copolymer (Sbs) With Psmentioning

confidence: 57%

“…Furthermore, the ionic aggregation impeded the diffusion of the block segment, and the extent of the block microphase separation decreased with the increase of sulfonation level and the strength of the ionic interaction. It is also mentioned that the ionomer blocks in the sNa-SEBS have poor mobility, even in solution compared with the sZn-SEBS [28,29] . Those previous reports support that the ionic aggregation in the sCs-PSb-f-PI film cast from THF/water and DMSO is stable under the thermal annealing at 140 ° C.…”

Section: Ps-b-poly(butadiene)-ps Block Copolymer (Sbs) With Psmentioning

confidence: 99%

Effect of solvents and thermal annealing on the morphology development of a novel block copolymer ionomer: a case study of sulfonated polystyrene-block-fluorinated polyisoprene

Hosoda¹,

Gido

Mays

et al. 2013

Journal of Polymer Engineering

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The morphologies of sulfonated polystyreneblock-fluorinated polyisoprene (s-PS-b-f-PI) were studied as functions of different kinds of solvents and thermal annealing, using transmission electron microscope microscopy (TEM), small angle X-ray scattering (SAXS) and intermediate angle X-ray diffraction (IMAXD). The film of the block copolymer ionomer with an acid form [sulfonated PS-b-fluorinated PI (sH-PS-b-f-PI)], which was cast from anhydrous tetrahydrofuran (THF), developed a well-ordered cylindrical morphology of the f-PI domains in the sH-PS matrix. The morphology was explained by the solubility parameter and the Bjerrum length. The morphology changed to that of a no longrange ordered structure, through thermal annealing. The result was different from the usual behavior of uncharged diblock copolymers and could have been due to the ionic cluster formation. The solution casting films of the block copolymer ionomer with a cesium neutralized form (sCs-PS-b-f-PI) were obtained from the mixed solvent of THF/ water (98/2, wt/wt) and DMSO. The ionic cluster formation in the film cast from the mixed solvent was hardly changed by annealing. The promotion of the ionic cluster formation by annealing was clearly observed in the film cast from DMSO. However, hindrance of microphase separation by the promotion of the ionic cluster formation was not confirmed in this study.

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Thermally Induced Microstructure Transitions in a Block Copolymer Ionomer

Cited by 26 publications

References 13 publications

Morphologies of block copolymers composed of charged and neutral blocks

Morphologies of block copolymers composed of charged and neutral blocks

Synthesis and Proton Conductivity of Partially Sulfonated Poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) Block Copolymers

Effect of solvents and thermal annealing on the morphology development of a novel block copolymer ionomer: a case study of sulfonated polystyrene-block-fluorinated polyisoprene

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