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The behavior of cross-linking polymer solutions as they transition from liquid-like to solid-like material in flow determines success or failure in several applications. Dilute polymer solutions flow easily, while concentrated polymers or crosslinked polymer gels can clog pores, nozzles, or channels. We have recently described a third regime of flow dynamics in polymers that occurs when cross-linking happens during flow: persistent intermittency. When a dilute alginate solution meets calcium at a Y-shaped microfluidic junction, a persistent and regular pattern of gel deposition and ablation emerges when driven at a constant volumetric flow rate. Chemical concentrations and flow rate control both the gel deposition and critical shear stress required to ablate the adhered gel. In this work, we provide an analytical framework to quantitatively describe the intermittent behavior as resulting from diffusively driven deposition in a high Peclet number flow. Fitting the experimental data shows that higher component concentrations lead to more efficient deposition and more swollen gels. Increasing the flow rate increases the deposition rate, but the resulting gels are much less swollen. Ablation occurs when applied shear stresses overcome either the adhesive energy of the gel or its yield stress. The shear stress required at ablation decreases with increased component concentrations. By correlating the results of the analytical analysis with bulk rheology measurements, we find that deposition efficiency increases with the stiffness of the gel formed in flow. Softer gels withstand higher shear stresses before ablation. Both deposition efficiency and gel stiffness increase in flow conditions nearing complete clogging.
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In situ polymer gelation in confined flow controls intermittent dynamics
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.
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- Award ID(s):
- 2239742
- PAR ID:
- 10503842
- Editor(s):
- Professor Ewa Gorecka, Associate Editor
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 20
- Issue:
- 8
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 1858 to 1868
- Subject(s) / Keyword(s):
- alginate hydrogels crosslinking polymers gelation in flow microfluidics deposition
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3SM01389H
