Salt-induced microphase separation in poly(ε-caprolactone)-b-poly(ethylene oxide) block copolymer

Huang, Jie; Tong, Zaizai; Zhou, Bing; Xu, Jun‐Ting; Fan, Zhiqiang

doi:10.1016/j.polymer.2013.03.070

Cited by 45 publications

(71 citation statements)

References 77 publications

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“…Wang et al 26 used small-angle neutron scattering (SANS) to directly measure χ eff on a polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) copolymer that was complexed with lithium chloride, while Naidu et al 11 used SAXS to measure χ eff on a polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) copolymer that was doped with lithium perchlorate. Young et al 10 and Huang et al 9 used domain spacing as a proxy to study χ eff in both an SEO copolymer that was mixed with several lithium salts and a poly(ε-caprolactone)-b-poly(ethylene oxide) (PCLb-PEO) that was complexed with lithium perchlorate. The effect of salt on χ eff was determined from order−disorder transition (ODT) measurements by Wanakule et al 13 using a series of SEO copolymers complexed with LiTFSI and by Gunkel et al 12 using both an SEO copolymer and a PS-b-P2VP copolymer complexed with lithium triflate.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Thermodynamics of Block Copolymers with and without Salt

2013

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Ion-containing block copolymers are of interest for applications such as electrolytes in rechargeable lithium batteries. The addition of salt to these materials is necessary to make them conductive; however, even small amounts of salt can have significant effects on the phase behavior of these materials and consequently on their ion-transport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the past decade. This feature article describes a comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations, and temperatures. The Flory-Huggins interaction parameter was determined by fitting small-angle X-ray scattering data of disordered systems to predictions based on the random phase approximation. Experiments on neat block copolymers revealed that the Flory-Huggins parameter is a strong function of chain length. Experiments on block copolymer/salt mixtures revealed a highly nonlinear dependence of the Flory-Huggins parameter on salt concentration. These findings are a significant departure from previous results and indicate the need for improved theories for describing thermodynamic interactions in neat and salt-containing block copolymers.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Thermodynamics of Block Copolymers with and without Salt

2013

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“…Recently, ion/block copolymers (BCPs) hybrids have become highly attractive materials due to their flexibility, process stability, self-assembling ability and novel features of inorganic components such as electronic, magnetic and optical properties [ 1 – 3 ]. Spatz and co-workers created fused silica substrates with nanopillars on both sides with 99.8% transmittance and 0.02% reflectance, which was helpful for many laser applications [ 4 ].…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene

Huang

Zhong

et al. 2017

Nanoscale Res Lett

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Ordered nanopatterns of triblock copolymer polystyrene-block-poly(2-vinylpyridine)-block- poly (ethylene oxide)(PS-b-P2VP-b-PEO) have been achieved by the addition of lithium chloride (LiCl). The morphological and structural evolution of PS-b-P2VP-b-PEO/LiCl thin films were systematically investigated by varying different experimental parameters, including the treatment for polymer solution after the addition of LiCl, the time scale of ultrasonic treatment and the molar ratio of Li+ ions to the total number of oxygen atoms (O) in PEO block and the nitrogen atoms (N) in P2VP block. When toluene was used as the solvent for LiCl, ordered nanopattern with cylinders or nanostripes could be obtained after spin-coating. The mechanism of nanopattern transformation was related to the loading of LiCl in different microdomains.

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“…Gunkel and Thurn‐Albrecht have reported a similar lithium concentration dependence of χ eff for the lithium salt LiCF 3 SO 3 embedded in both PS‐ b ‐PEO and polystyrene‐ block ‐poly(2‐vinylpyridine) (PS‐ b ‐P2VP) DBCs 10. Other related amphiphilic BC systems, including polystyrene‐ block ‐polymethyl methacrylate (PS‐ b ‐PMMA) DBC complexed with lithium chloride,11 PS‐ b ‐P2VP DBC complexed with lithium perchlorate,9c and poly ε‐caprolactone‐ block ‐polyethylene oxide (PCL‐ b ‐EO) complexed with lithium perchlorate,9d have revealed χ eff behavior similar to that of the salt concentration. Quite unexpectedly, Teran and Balsara recently indicated a nonlinear dependence of χ eff on the salt concentration for a PS‐ b ‐PEO DBC with a low molecular weight (<14 kg mol −1 ) 2j.…”

Section: Introductionmentioning

confidence: 99%

Lithium‐Salt‐Containing High‐Molecular‐Weight Polystyrene‐block‐Polyethylene Oxide Block Copolymer Films

et al. 2015

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Ionic conductivity in relation to the morphology of lithium-doped high-molecular-weight polystyrene-block-polyethylene oxide (PS-b-PEO) diblock copolymer films was investigated as solid-state membranes for lithium-ion batteries. The tendency of the polyethylene (PEO) block to crystallize was highly suppressed by increasing both the salt-doping level and the temperature. The PEO crystallites completely vanished at a salt-doping ratio of Li/EO>0.08, at which the PEO segments were hindered from entering the crystalline unit of the PEO chain. A kinetically trapped lamella morphology of PS-b-PEO was observed, due to PEO crystallization. The increase in the lamella spacing with increasing salt concentration was attributed to the conformation of the PEO chain rather than the volume contribution of the salt or the previously reported increase in the effective interaction parameter. Upon loading the salt, the PEO chains changed from a compact/highly folded conformation to an amorphous/expanded-like conformation. The ionic conductivity was enhanced by amorphization of PEO and thereby the mobility of the PEO blocks increased upon increasing the salt-doping level.

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Salt-induced microphase separation in poly(ε-caprolactone)-b-poly(ethylene oxide) block copolymer

Cited by 45 publications

References 77 publications

Thermodynamics of Block Copolymers with and without Salt

Thermodynamics of Block Copolymers with and without Salt

Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene

Lithium‐Salt‐Containing High‐Molecular‐Weight Polystyrene‐block‐Polyethylene Oxide Block Copolymer Films

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