Oil‐in‐water droplets stabilized with polymer zwitterions (PZWs) exhibit salt‐responsive aggregation–disaggregation behavior. Here, a method to shape these droplets is described, starting from their aggregated state, into supracolloidal fibers by simply extruding them into aqueous media. The effect of salt concentration, in both the initial emulsion and the aqueous medium, on the ability of the emulsions to form fibers is examined. After fiber formation, a transition from well‐defined macroscopic structures to noninteracting droplet dispersions can be triggered, simply by increasing the salt concentration of the aqueous environment. The interdroplet energy of adhesion and emulsion rheology correlate qualitatively with salt concentration and thus impact the ability of the emulsions to be shaped by extrusion. The interdroplet adhesion is dependent on both salt concentration and polymer composition, which allows tailoring of conditions to trigger fiber disaggregation. Finally, fibers with variable compositions along their length are prepared by sequential loading and extrusion of emulsions containing oil phases of differing densities.
Polymer zwitterions are generally regarded as hydrophilic and repellant or “slippery” materials. Here, a case is described in which the polymer zwitterion structure is tailored to decrease water solubility, stabilize emulsion droplets, and promote interdroplet adhesion. Harnessing the upper critical solution temperature of sulfonium‐ and ammonium‐based polymer zwitterions in water, adhesive droplets are prepared by adding organic solvent to an aqueous polymer solution at elevated temperature, followed by agitation to induce emulsification. Droplet aggregation is observed as the mixture cools. Variation of salt concentration, temperature, polymer concentration, and polymer structure modulates these interdroplet interactions, resulting in distinct changes in emulsion stability and fluidity. Under attractive conditions, emulsions encapsulating 50–75% oil undergo gelation. By contrast, emulsions prepared under conditions where droplets are nonadhesive remain fluid and, for oil fractions exceeding 0.6, coalescence is observed. The uniquely reactive nature of the selected zwitterions allows their in situ modification and affords a route to chemically trigger deaggregation and droplet dispersion. Finally, experiments performed in a microfluidic device, in which droplets are formed under conditions that either promote or suppress adhesion, confirm the salt‐responsive character of these emulsions and the persistence of adhesive interdroplet interactions under flow.
more » « less- NSF-PAR ID:
- 10038701
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 29
- Issue:
- 38
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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