More Like this

1. In situ polymer gelation in confined flow controls intermittent dynamics

   https://doi.org/10.1039/D3SM01389H  

   Smith, Barrett T.; Hashmi, Sara M. (February 2024, Soft Matter)

   Professor Ewa Gorecka, Associate Editor (Ed.)

   Polymer flows through pores, nozzles and other small channels govern engineered and naturally occurring dynamics in many processes, from 3D printing to oil recovery in the earth's subsurface to a wide variety of biological flows. The crosslinking of polymers can change their material properties dramatically, and it is advantageous to know a priori whether or not crosslinking polymers will lead to clogged channels or cessation of flow. In this study, we investigate the flow of a common biopolymer, alginate, while it undergoes crosslinking by the addition of a crosslinker, calcium, driven through a microfluidic channel at constant flow rate. We map the boundaries defining complete clogging and flow as a function of flow rate, polymer concentration, and crosslinker concentration. Interestingly, the boundaries of the dynamic behavior qualitatively match the thermodynamic jamming phase diagram of attractive colloidal particles. That is, polymer clogging occurs in a region analogous to colloids in a jammed state, while the polymer flows in regions corresponding to colloids in a liquid phase. However, between the dynamic regimes of complete clogging and unrestricted flow, we observe a remarkable phenomenon in which the crosslinked polymer intermittently clogs the channel. This pattern of deposition and removal of a crosslinked gel is simultaneously highly reproducible, long-lasting, and controllable by system parameters. Higher concentrations of polymer and cross-linker result in more frequent ablation, while gels formed at lower component concentrations ablate less frequently. Upon ablation, the eluted gel maintains its shape, resulting in micro-rods several hundred microns long. Our results suggest both rich dynamics of intermittent flows in crosslinking polymers and the ability to control them. 

   more » « less
2. 3D microfluidics via cyclic olefin polymer-based in situ direct laser writing

   https://doi.org/10.1039/C9LC00542K  

   Alsharhan, Abdullah T.; Acevedo, Ruben; Warren, Roseanne; Sochol, Ryan D. (August 2019, Lab on a Chip)

   In situ direct laser writing ( is DLW) strategies that facilitate the printing of three-dimensional (3D) nanostructured components directly inside of, and fully sealed to, enclosed microchannels are uniquely suited for manufacturing geometrically complex microfluidic technologies. Recent efforts have demonstrated the benefits of using micromolding and bonding protocols for is DLW; however, the reliance on polydimethylsiloxane (PDMS) leads to limited fluidic sealing ( e.g. , operational pressures <50–75 kPa) and poor compatibility with standard organic solvent-based developers. To bypass these issues, here we explore the use of cyclic olefin polymer (COP) as an enabling microchannel material for is DLW by investigating three fundamental classes of microfluidic systems corresponding to increasing degrees of sophistication: (i) “2.5D” functionally static fluidic barriers (10–100 μm in height), which supported uncompromised structure-to-channel sealing under applied input pressures of up to 500 kPa; (ii) 3D static interwoven microvessel-inspired structures (inner diameters < 10 μm) that exhibited effective isolation of distinct fluorescently labelled microfluidic flow streams; and (iii) 3D dynamically actuated microfluidic transistors, which comprised bellowed sealing elements (wall thickness = 500 nm) that could be actively deformed via an applied gate pressure to fully obstruct source-to-drain fluid flow. In combination, these results suggest that COP-based is DLW offers a promising pathway to wide-ranging fluidic applications that demand significant architectural versatility at submicron scales with invariable sealing integrity, such as for biomimetic organ-on-a-chip systems and integrated microfluidic circuits. 

   more » « less
3. Polymer blend-filled nanoparticle films via monomer-driven infiltration of polymer and photopolymerization

   https://doi.org/10.1039/C7ME00099E  

   Qiang, Yiwei; Manohar, Neha; Stebe, Kathleen J.; Lee, Daeyeon (January 2018, Molecular Systems Design & Engineering)

   Incorporation of nanoparticles into polymer blend films can lead to a synergistic combination of properties and functionalities. Adding a large concentration of nanoparticles into a polymer blend matrix via conventional melting or solution blending techniques, however, is challenging due to the tendency of particles to aggregate. Herein, we report a straightforward approach to generate polymer blend/nanoparticle ternary composite films with extremely high loadings of nanoparticles based on monomer-driven infiltration of polymer and photopolymerization. The fabrication process consists of three steps: (1) preparing a bilayer with a nanoparticle (NP) layer atop a polymer layer, (2) annealing of the bilayer with a vapour mixture of a monomer and a photoinitiator, which undergoes capillary condensation and imparts mobility to the polymer layer and (3) exposing this film to UV light to induce photopolymerization of the monomer. The monomer used in this process is chemically different from the repeat unit of the polymer in the bilayer and is a good solvent for the polymer. The second step leads to the infiltration of the plasticized polymer, and the third step results in a blend of two polymers in the interstices of the nanoparticle layer. By varying the thickness ratio of the polymer and nanoparticle layers in the initial bilayers and changing the UV exposure duration, the volume fraction of the two polymers in the composite films can be adjusted. This versatile approach enables the design and engineering of a new class of nanocomposite films that contain a nanoscale-blend of two polymers in the interstices of a nanoparticle film, which could have combinations of unique mechanical and transport properties desirable for advanced applications such as membrane separations, conductive composite films and solar cells. Moreover, these polymer blend-filled nanoparticle films could serve as model systems to study the effect of confinement on the miscibility and morphology of polymer blends. 

   more » « less
4. Combined Mixing and Dynamical Origins of T _g Alterations Near Polymer–Polymer Interfaces

   https://doi.org/10.1021/acs.macromol.2c01621  

   Ghanekarade, Asieh; Simmons, David S. (January 2023, Macromolecules)
5. Polymer N -Heterocyclic Carbene (NHC) Ligands for Silver Nanoparticles

   https://doi.org/10.1021/acsami.2c17706  

   Wei, Zichao; Mullaj, Kayceety; Price, Aleisha; Wei, Kecheng; Luo, Qiang; Thanneeru, Srinivas; Sun, Shouheng; He, Jie (December 2022, ACS Applied Materials & Interfaces)