Solvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticles

Handle URI:
http://hdl.handle.net/10754/599670
Title:
Solvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticles
Authors:
Anyfantakis, Manos; Bourlinos, Athanasios; Vlassopoulos, Dimitris; Fytas, George; Giannelis, Emmanuel; Kumar, Sanat K.
Abstract:
We explore the role of the solvent medium on the interplay between gelation and phase separation in suspensions of organosilicate planar hybrids grafted with hydrocarbon chains. We establish their phase diagram by means of dynamic light scattering, rheology and visual observations, and different routes to gelation, depending on the solvent used. In agreement with earlier works, the solvent quality for the grafted chains at a given temperature controls the balance between attractions and repulsions, and hence the phase diagram of the nanoparticles and their tendency to gel. Here we show how to tune the suspension state and hence its rheology. For decane, a good solvent for the hydrocarbon chains, gelation occurs at rather low volume fractions in the presence of phase separation. This is due to the interdigitation of solvent molecules with the grafted chains, resulting in their crystalline packing that promotes the attraction between particles. For toluene, a solvent of reduced quality for the hydrocarbon chains, no interdigitation takes place, and hence gelation is triggered by clustering at higher volume fractions before phase separation. Our results support the generic picture of complex kinetic arrest/phase separation interplay in soft matter, where phase separation can proceed, be interrupted or be completely inhibited. A number of interesting possibilities for tailoring the rheology of grafted colloidal systems emerge. © 2009 The Royal Society of Chemistry.
Citation:
Anyfantakis M, Bourlinos A, Vlassopoulos D, Fytas G, Giannelis E, et al. (2009) Solvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticles. Soft Matter 5: 4256. Available: http://dx.doi.org/10.1039/b911244h.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Soft Matter
KAUST Grant Number:
KUS-C1-018-02
Issue Date:
2009
DOI:
10.1039/b911244h
Type:
Article
ISSN:
1744-683X; 1744-6848
Sponsors:
We would like to thank B. Mueller and E. Pavlopoulou for the refractive index contrast and the SAXS measurements, respectively, as well as A. Larsen and D. Kendristaki for assistance in some PCS and rheology measurements. We are grateful to B. Loppinet for helpful discussions and to J. K. G. Dhont for insightful comments and for bringing to our attention refs. 38 and 73. This work was supported in part by the EU NoE-Softcomp (NMP3-CT-2004-502235). EPG acknowledges the support of Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST).
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Full metadata record

DC FieldValue Language
dc.contributor.authorAnyfantakis, Manosen
dc.contributor.authorBourlinos, Athanasiosen
dc.contributor.authorVlassopoulos, Dimitrisen
dc.contributor.authorFytas, Georgeen
dc.contributor.authorGiannelis, Emmanuelen
dc.contributor.authorKumar, Sanat K.en
dc.date.accessioned2016-02-28T06:07:10Zen
dc.date.available2016-02-28T06:07:10Zen
dc.date.issued2009en
dc.identifier.citationAnyfantakis M, Bourlinos A, Vlassopoulos D, Fytas G, Giannelis E, et al. (2009) Solvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticles. Soft Matter 5: 4256. Available: http://dx.doi.org/10.1039/b911244h.en
dc.identifier.issn1744-683Xen
dc.identifier.issn1744-6848en
dc.identifier.doi10.1039/b911244hen
dc.identifier.urihttp://hdl.handle.net/10754/599670en
dc.description.abstractWe explore the role of the solvent medium on the interplay between gelation and phase separation in suspensions of organosilicate planar hybrids grafted with hydrocarbon chains. We establish their phase diagram by means of dynamic light scattering, rheology and visual observations, and different routes to gelation, depending on the solvent used. In agreement with earlier works, the solvent quality for the grafted chains at a given temperature controls the balance between attractions and repulsions, and hence the phase diagram of the nanoparticles and their tendency to gel. Here we show how to tune the suspension state and hence its rheology. For decane, a good solvent for the hydrocarbon chains, gelation occurs at rather low volume fractions in the presence of phase separation. This is due to the interdigitation of solvent molecules with the grafted chains, resulting in their crystalline packing that promotes the attraction between particles. For toluene, a solvent of reduced quality for the hydrocarbon chains, no interdigitation takes place, and hence gelation is triggered by clustering at higher volume fractions before phase separation. Our results support the generic picture of complex kinetic arrest/phase separation interplay in soft matter, where phase separation can proceed, be interrupted or be completely inhibited. A number of interesting possibilities for tailoring the rheology of grafted colloidal systems emerge. © 2009 The Royal Society of Chemistry.en
dc.description.sponsorshipWe would like to thank B. Mueller and E. Pavlopoulou for the refractive index contrast and the SAXS measurements, respectively, as well as A. Larsen and D. Kendristaki for assistance in some PCS and rheology measurements. We are grateful to B. Loppinet for helpful discussions and to J. K. G. Dhont for insightful comments and for bringing to our attention refs. 38 and 73. This work was supported in part by the EU NoE-Softcomp (NMP3-CT-2004-502235). EPG acknowledges the support of Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST).en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleSolvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticlesen
dc.typeArticleen
dc.identifier.journalSoft Matteren
dc.contributor.institutionFoundation for Research and Technology-Hellas, Institute of Electronic Structure and Laser, Heraklion, Greeceen
dc.contributor.institutionPanepistimio Kritis, Rethymnon, Greeceen
dc.contributor.institutionCornell University, Ithaca, United Statesen
dc.contributor.institutionColumbia University in the City of New York, New York, United Statesen
kaust.grant.numberKUS-C1-018-02en
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