Rheological modifiers tune product rheology with a small amount of material. To effectively use rheological modifiers, characterizing the rheology of the system at different compositions is crucial. Two colloidal rod system, hydrogenated castor oil and polyamide, are characterized in a formulation that includes a surfactant (linear alkylbenzene sulfonate) and a depletant (polyethylene oxide). We characterize both rod systems using multiple particle tracking microrheology (MPT) and bulk rheology and build phase diagrams over a large component composition space. In MPT, fluorescent particles are embedded in the sample and their Brownian motion is measured and related to rheological properties. From MPT, we determine that in both systems: (1) microstructure is not changed with increasing colloid concentration, (2) materials undergo a sol–gel transition as depletant concentration increases and (3) the microstructure changes but does not undergo a phase transition as surfactant concentration increases in the absence of depletant. When comparing MPT and bulk rheology results different trends are measured. Using bulk rheology we observe: (1) elasticity of both systems increase as colloid concentration increases and (2) the storage modulus does not change when PEO or LAS concentration is increased. The differences measured with MPT and bulk rheology are likely due to differences in sensitivity and measurement method. This work shows the utility of using both techniques together to fully characterize rheological properties over a large composition space. These gelation phase diagrams will provide a guide to determine the composition needed for desired rheological properties and eliminate trial-and-error experiments during product formulation.
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High-throughput microscopy to determine morphology, microrheology, and phase boundaries applied to phase separating coacervates
Evolution of composition, rheology, and morphology during phase separation in complex fluids is highly coupled to rheological and mass transport processes within the emerging phases, and understanding this coupling is critical for materials design of multiphase complex fluids. Characterizing these dependencies typically requires careful measurement of a large number of equilibrium and transport properties that are difficult to measure in situ as phase separation proceeds. Here, we propose and demonstrate a high-throughput microscopy platform to achieve simultaneous, in situ mapping of time-evolving morphology and microrheology in phase separating complex fluids over a large compositional space. The method was applied to a canonical example of polyelectrolyte complex coacervation, whereby mixing of oppositely charged species leads to liquid–liquid phase separation into distinct solute-dense and dilute phases. Morphology and rheology were measured simultaneously and kinetically after mixing to track the progression of phase separation. Once equilibrated, the dense phase viscosity was determined to high compositional accuracy using passive probe microrheology, and the results were used to derive empirical relationships between the composition and viscosity. These relationships were inverted to reconstruct the dense phase boundary itself, and further extended to other mixture compositions. The resulting predictions were validated by independent equilibrium compositional measurements. This platform paves the way for rapid screening and formulation of complex fluids and (bio)macromolecular materials, and serves as a critical link between formulation and rheology for multi-phase material discovery.
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- NSF-PAR ID:
- 10322297
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 18
- Issue:
- 15
- ISSN:
- 1744-683X
- 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/D1SM01763B
