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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Kočí, Jan | Prague |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Ali, M. A. |
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| Rančić, M. |
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| Azevedo, Nuno Monteiro |
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Schmitt, Adam K.
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Publications (3/3 displayed)
- 2017Order and Disorder in High x/Low N, Broad Dispersity ABA Triblock Polymerscitations
- 2014Phase behavior of poly(4-hydroxystyrene-block-styrene) synthesized by living anionic polymerization of an acetal protected monomercitations
- 2013Bulk and thin film morphological behavior of broad dispersity poly(styrene-b-methyl methacrylate) diblock copolymerscitations
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article
Order and Disorder in High x/Low N, Broad Dispersity ABA Triblock Polymers
Abstract
<p>Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (M<sub>n</sub> = 4.5-17.7 kg/mol; D= M<sub>w</sub>/M<sub>n</sub> = 1.72-1.88) and narrow dispersity L end blocks (M<sub>n</sub> = 0.6-15.3 kg/mol; D= 1.10-1.21) with volume fractions 0.26 ≤ f<sub>B</sub> ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength xN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction xN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low x/high N ABA triblocks, the present study indicates that broad B block dispersity in related high x/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.</p>