skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Friday, November 14 until 2:00 AM ET on Saturday, November 15 due to maintenance. We apologize for the inconvenience.


Title: Building Supracolloidal Fibers from Zwitterion‐Stabilized Adhesive Emulsions
Abstract 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.  more » « less
Award ID(s):
1740630
PAR ID:
10075790
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
28
Issue:
45
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Advanced synthetic materials are needed to produce nano‐ and mesoscale structures that function autonomously, catalyze reactions, and convert chemical energy into motion. This paper describes supracolloidal fiber‐like structures that are composed of self‐adhering, or “sticky,” oil‐in‐water emulsion droplets. Polymer zwitterion surfactants serve as the key interfacial components of these materials, enabling multiple functions simultaneously, including acting as droplet‐stabilizing surfactants, interdroplet adhesives, and building blocks of the fibers. This fiber motion, a surprising additional feature of these supracolloidal structures, is observed at the air–water interface and hinged on the chemistry of the polymer surfactant. The origin of this motion is hypothesized to involve transport of polymer from the oil–water interface to the air–water interface, which generates a Marangoni (interfacial) stress. Harnessing this fiber motion with functional polymer surfactants, and selection of the oil phase, produced worm‐like objects capable of rotation, oscillation, and/or response to external fields. Overall, these supracolloidal fibers fill a design gap between self‐propelled nano/microscale particles and macroscale motors, and have the potential to serve as new components of soft, responsive materials structures. 
    more » « less
  2. A novel castor oil/water/ethanol Pickering emulsion, stabilized by magnetic nanoparticles (NPs), was developed to allow on-demand demulsification by an external magnetic field for the extraction of ethanol from aqueous solution using the castor oil. The emulsion was stabilized by Fe3O4-coated cellulose nanocrystals (CNC@Fe3O4) and lignin-coated Fe3O4 NPs (lignin@Fe3O4). The stability of the emulsions was investigated at various castor oil to ethanol-water ratios (50/50 and 70/30), various NP concentrations, and ethanol concentrations in the aqueous phase. The magnetically controlled demulsification ability of the emulsions was investigated by using a permanent magnet. The results showed that the 70/30 emulsions were more stable than the 50/50 emulsions for all the ethanol concentrations. Moreover, increasing the NP concentration increased the emulsion stability and hence, 1 w/v% NPs concentration provided the more stable systems. However, all the emulsions were successfully broken by the permanent magnet. Yet, the presence of ethanol improves the ability of the external magnetic field to demulsify these dispersions. Furthermore, the used hybrid NPs were recovered and recycled for three cycles. The recycled NPs were characterized with X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) indicating that they retained their saturation magnetization and crystalline structure, demonstrating their lack of degradation over multiple recycling cycles. This study facilitates the exploration of innovative two-phase Pickering emulsions comprising three distinct liquid components and their utilization in liquid-liquid extraction processes. 
    more » « less
  3. This work examines the functional dependence of the efficiency of separation of oil−water emulsions on surfactant adsorption abilities of high surface area polymer gels. The work also develops an understanding of the factors and steps that are involved in emulsion separation processes using polymer gels. The work considers four polymer gels offering different surface energy values, namely, syndiotactic polystyrene (sPS), polyimide (PI), polyurea (PUA), and silica. The data reveal that surfactant adsorption abilities directly control the emulsion separation performance. The gels of sPS and PI destabilize the emulsions due to significant surfactant adsorption. The surfactant-lean oil droplets are then absorbed in the pores of sPS and PI gels due to the preferential wettability of the oil phase. The PUA and silica gels are more hydrophilic and show a lower surfactant adsorption ability. These gels cannot effectively remove the surfactant molecules from the emulsions, leading to a poor emulsion separation performance. The study uses simulation data to understand the adsorption characteristics of two poly(ethylene oxide)- poly(propylene oxide)-poly(ethylene oxide) block copolymer surfactants. The simulation results are used for the interpretation of emulsion separation performance by the gels. 
    more » « less
  4. We report a microfluidic droplet generator which can produce single and compound droplets using a 3D axisymmetric co-flow structure. The design considered for the fabrication of the device integrated a user-friendly and cost-effective 3D printing process. To verify the performance of the device, single and compound emulsions of deionized water and mineral oil were generated and their features such as size, generation frequency, and emulsion structures were successfully characterized. In addition, the generation of bio emulsions such as alginate and collagen aqueous droplets in mineral oil was demonstrated in this study. Overall, the monolithic 3D printed axisymmetric droplet generator could offer any user an accessible and easy-to-utilize device for the generation of single and compound emulsions. 
    more » « less
  5. Emulsion templates can produce a wide range of unique microstructures via solidification of the continuous phase. Some of these structures result in unique, fluid-filled composites reminiscent of biological tissue when the templating droplets develop into closed-cell structures. However, the state-of-the-art falls short in replicating the mechanical and functional response of biological structures due to stiff, fragile, and bio-incompatible materials while lacking systematic processing parameters. This article describes the synthesis of high internal phase, closed-cell, polydimethylsiloxane (PDMS) elastomeric foams which simultaneously achieve biocompatibility, mechanical robustness, flexibility, and selective permeability. Water-in-oil high internal phase emulsions (HIPEs) stabilized by silica nano-particles (SNPs) provide the microstructural template, resulting in a >74% by volume aqueous phase (up to 82%). To overcome the prohibitive barrier to HIPE formation when using a mechanically-superior, but highly viscous commercial PDMS kit, we produce HIPE templates via centrifugation of low internal phase emulsions (LIPEs, <30% by volume dispersed phase). This oil phase crosslinks into an aqueous-filled (water + glycerol + NaCl) elastomeric composite. The composite's microstructural dependence on viscosity ratio, mixing speed, emulsifier concentration, and centrifugal force are systematically characterized. The resulting microstructured, fluid-filled elastomer composites exhibit mechanically robust and highly flexible behavior due to the excellent properties of the PDMS continuous phase. 
    more » « less