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.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Who wins the race near the interface? Stratification of colloids, nano-surfactants, and others
The diffusion of colloids, nanoparticles, and small molecules near the gas–liquid interface presents interesting multiphase transport phenomena and unique opportunities for understanding interactions near the surface and interface. Stratification happens when different species preside over the interfaces in the final dried coating structure. Understanding the principles of stratification can lead to emerging technologies for materials’ fabrication and has the potential to unlock innovative industrial solutions, such as smart coatings and drug formulations for controlled release. However, stratification can be perplexing and unpredictable. It may involve a complicated interplay between particles and interfaces. The surface chemistry and solution conditions are critical in determining the race of particles near the interface. Current theory and simulation cannot fully explain the observations in some experiments, especially the newly developed stratification of nano-surfactants. Here, we summarize the efforts in the experimental work, theory, and simulation of stratification, with an emphasis on bridging the knowledge gap between our understanding of surface adsorption and bulk diffusion. We will also propose new mechanisms of stratification based on recent observations of nano-surfactant stratification. More importantly, the discussions here will lay the groundwork for future studies beyond stratification and nano-surfactants. The results will lead to the fundamental understanding of nanoparticle interactions and transport near interfaces, which can profoundly impact many other research fields, including nanocomposites, self-assembly, colloidal stability, and nanomedicine.  more » « less
Award ID(s):
1939362
PAR ID:
10416999
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Journal of Applied Physics
Volume:
132
Issue:
11
ISSN:
0021-8979
Page Range / eLocation ID:
110901
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; (, Chemical Science)
    null (Ed.)
    Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection–absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C–F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C–H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science. 
    more » « less
  2. ; ; ; (, E3S Web of Conferences)
    McCartney, J.S.; Tomac, I. (Ed.)
    Immiscible multiphase flow in porous media is largely affected by interfacial properties, manifested in contact angle and surface tension. The gas-liquid surface tension can be significantly altered by suspended particles at the interface. Particle-laden interfaces have unique properties, for example, a lower surface tension of interfaces laden with surfactants or nanoparticles. This study investigates the impacts of a motile bacterium Escherichia coli ( E. coli , strain ATCC 9637) on the air-water surface tension. Methods of the maximum bubble pressure, the du Noüy ring, and the pendant droplet are used to measure the surface tension of the motile-bacteria-laden interfaces. Measured surface tension remains independent to the E. coli concentration when using the maximum bubble pressure method, decreases with increased E. coli concentration in the du Noüy ring method, and presents time-dependent changes by the pendant drop method. The analyses show that the discrepancies may come from the different convection-diffusion processes of E. coli in the flow among various testing methods. 
    more » « less
  3. ; ; ; ; (, Macromolecular Rapid Communications)
    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
  4. ; ; ; ; (, Physical Chemistry Chemical Physics)
    Description: Mechanistic analysis of ion desorption from glutaric acid particles used in the development of surface-sensitive mass spectroscopy ionization methods. Abstract: Ionization via desorption of charged analytes from the surface of solid amorphous glutaric acid particles, without the assistance of an external energy source, has been shown to be a promising method that can be coupled to mass spectrometry. We conduct mechanistic studies of the later stages of this ionization process using atomistic molecular dynamics. Our analysis focuses on the hydrogen bonding, diffusion, and ion desorption from nano-aggregates of glutaric acid. These nano-aggregates exhibit an extended H-bonded network, often comprising H-bonded chains, linear dimeric assemblies, and occasionally cyclic trimeric assemblies. These local structures serve as centers for proton transfer reactions. The intermediate hydrocarbon chain between the proton-carrying oxygen sites prevents proton diffusion over a long distance unless there is significant translational or rotational movement of the proton-carrying diacid molecule. Our calculations show that diffusion on the surface is an order of magnitude faster than in the core of the nano-aggregate, which aids effective proton transfer on the particle's exterior. We find that ionic species desorb from the aggregate's surface through independent evaporation events of small clusters, where the ion is coordinated by only a few glutaric acid molecules. Near the nano-aggregate's Rayleigh limit, jets capable of releasing multiple ions were not observed. These observations suggest a more general ion-evaporation mechanism that applies to low-dielectric particles of various sizes, complementing the original ion-evaporation mechanism proposed for aqueous droplets with an approximate radius of 10–15 nm. The combined evidence from molecular modeling presented here and the thermodynamic properties of solid and supercooled liquid glutaric acid indicates that the stronger signals of glutaric acid observed in the mass spectra, relative to other experimentally tested diacids, can be attributed to its significantly lower melting point and the reduced enthalpy of vaporization of its amorphous state compared to other tested diacids. 
    more » « less
  5. ; (, Annual Review of Fluid Mechanics)
    Density stratification due to temperature or salinity variations greatly influences the flow around and the sedimentation of objects such as particles, drops, bubbles, and small organisms in the atmosphere, oceans, and lakes. Density stratification hampers the vertical flow and substantially affects the sedimentation of an isolated object, the hydrodynamic interactions between a pair of objects, and the collective behavior of suspensions in various ways, depending on the relative magnitude of stratification, inertia (advection), and viscous (diffusion) effects. This review discusses these effects and their hydrodynamic mechanisms in some commonly observed fluid–particle transport phenomena in oceans and the atmosphere. Physical understanding of these mechanisms can help us better model these phenomena and, hence, predict their geophysical, engineering, ecological, and environmental implications. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email