skip to main content

Title: Emergence of viscosity and dissipation via stochastic bonds
“Viscosity is the most ubiquitous dissipative mechanical behavior” (Maugin, 1999). Despite its ubiquity, even for those systems where the mechanisms causing viscous and other forms of dissipation are known there are only a few quantitative models that extract the macroscopic rheological response from these microscopic mechanisms. One such mechanism is the stochastic breaking and forming of bonds which is present in polymer networks with transient cross-links, strong inter-layer bonding between graphene sheets, and sliding dry friction. In this paper we utilize a simple yet flexible model to show analytically how stochastic bonds can induce an array of rheological behaviors at the macroscale. We find that varying the bond interactions induces a Maxwell-type macroscopic material behavior with Newtonian viscosity, shear thinning, shear thickening, or solid like friction when subjected to shear at constant rates. When bond rupture is independent of the force applied, Newtonian viscosity is the predominant behavior. When bond breaking is accelerated by the applied force, a shear thinning response becomes most prevalent. Further connections of the macroscopic response to the interaction potential and rates of bonding and unbonding are illustrated through phase diagrams and analysis of limiting cases. Finally, we apply this model to polymer networks and to more » experimental data on “solid bridges” in polydisperse granular media. We imagine possible applications to material design through engineering bonds with specific interactions to bring about a desired macroscopic behavior. « less
; ; ;
Award ID(s):
Publication Date:
Journal Name:
Journal of the mechanics and physics of solids
Sponsoring Org:
National Science Foundation
More Like this
  1. Since their inception, hydrogels have gained popularity among multiple fields, most significantly in biomedical research and industry. Due to their resemblance to biological tribosystems, a significant amount of research has been conducted on hydrogels to elucidate biolubrication mechanisms and their possible applications as replacement materials. This review is focused on lubrication mechanisms and covers friction models that have attempted to quantify the complex frictional characteristics of hydrogels. From models developed on the basis of polymer physics to the concept of hydration lubrication, assumptions and conditions for their applicability are discussed. Based on previous models and our own experimental findings, we propose the viscous-adhesive model for hydrogel friction. This model accounts for the effects of confinement of the polymer network provided by a solid surface and poroelastic relaxation as well as the (non) Newtonian shear of a complex fluid on the frictional force and quantifies the frictional response of hydrogels-solid interfaces. Finally, the review delineates potential areas of future research based on the current knowledge.
  2. Nanoclay–polymer shear-thinning composites are designed for a broad range of biomedical applications, including tissue engineering, drug delivery, and additive biomanufacturing. Despite the advances in clay–polymer injectable nanocomposites, colloidal properties of layered silicates are not fully considered in evaluating the in vitro performance of shear-thinning biomaterials (STBs). Here, as a model system, we investigate the effect of ions on the rheological properties and injectability of nanoclay–gelatin hydrogels to understand their behavior when prepared in physiological media. In particular, we study the effect of sodium chloride (NaCl) and calcium chloride (CaCl 2 ), common salts in phosphate buffered saline (PBS) and cell culture media ( e.g. , Dulbecco's Modified Eagle's Medium, DMEM), on the structural organization of nanoclay (LAPONITE® XLG-XR, a hydrous lithium magnesium sodium silicate)-polymer composites, responsible for the shear-thinning properties and injectability of STBs. We show that the formation of nanoclay–polymer aggregates due to the ion-induced shrinkage of the diffuse double layer and eventually the liquid–solid phase separation decrease the resistance of STB against elastic deformation, decreasing the yield stress. Accordingly, the stress corresponding to the onset of structural breakdown (yield zone) is regulated by the ion type and concentration. These results are independent of the STB composition and canmore »directly be translated into the physiological conditions. The exfoliated nanoclay undergoes visually undetectable aggregation upon mixing with gelatin in physiological media, resulting in heterogeneous hydrogels that phase separate under stress. This work provides fundamental insights into nanoclay–polymer interactions in physiological environments, paving the way for designing clay-based injectable biomaterials.« less
  3. Proper pain management is well understood to be one of the fundamental aspects of a healthy postoperative recovery in conjunction with mobility and nutrition. Approximately, 10% of patients prescribed opioids after surgery continue to use opioids in the long-term and as little as 10 days on opioids can result in addiction. In an effort to provide physicians with an alternative pain management technique, this work evaluates the material properties of a novel local anesthetic delivery system designed for controlled release of bupivacaine for 72 hours. The formulation utilizes solid-lipid microparticles that encapsulate the hydrophobic molecule bupivacaine in its free-base form. The lipid microparticles are suspended in a non-crosslinked hyaluronic acid hydrogel, which acts as the microparticle carrier. Two different particle manufacturing techniques, milling and hot homogenization, were evaluated in this work. The hot homogenized particles had a slower and more controlled release than the milled particles. Rheological techniques revealed that the suspension remains a viscoelastic fluid when loaded with either particle type up to 25% (w/v) particles densities. Furthermore, the shear thinning properties of the suspension media, hyaluronic acid hydrogel, were conserved when bupivacaine-loaded solid-lipid microparticles were loaded up to densities of 25% (w/v) particle loading. The force during injection wasmore »measured for suspension formulations with varying hyaluronic acid hydrogel concentrations, particle densities, particle types and particle sizes. The results indicate that the formulation viscosity is highly dependent on particle density, but hyaluronic acid hydrogel is required for lowering injection forces as well as minimizing clogging events.

    « less
  4. Three-phase suspensions, of liquid that suspends dispersed solid particles and gas bubbles, are common in both natural and industrial settings. Their rheology is poorly constrained, particularly for high total suspended fractions (≳0.5). We use a dam-break consistometer to characterize the rheology of suspensions of (Newtonian) corn syrup, plastic particles and CO 2 bubbles. The study is motivated by a desire to understand the rheology of magma and lava. Our experiments are scaled to the volcanic system: they are conducted in the non-Brownian, non-inertial regime; bubble capillary number is varied across unity; and bubble and particle fractions are 0 ≤  ϕ gas  ≤ 0.82 and 0 ≤  ϕ solid  ≤ 0.37, respectively. We measure flow-front velocity and invert for a Herschel–Bulkley rheology model as a function of ϕ gas , ϕ solid , and the capillary number. We find a stronger increase in relative viscosity with increasing ϕ gas in the low to intermediate capillary number regime than predicted by existing theory, and find both shear-thinning and shear-thickening effects, depending on the capillary number. We apply our model to the existing community code for lava flow emplacement, PyFLOWGO, and predict increased viscosity and decreased velocity compared with current rheological models, suggesting existing models may notmore »adequately account for the role of bubbles in stiffening lavas.« less
  5. The influence of external factors, including temperature, storage, aging, time, and shear rate, on the general rheological behavior of raw human milk is investigated. Rotational and oscillatory experiments were performed. Human milk showed non-Newtonian, shear-thinning, thixotropic behavior with both yield and flow stresses. Storage and aging increased milk density and decreased viscosity. In general, increases in temperature lowered density and viscosity with periods of inconsistent behavior noted between 6–16 ∘ C and over 40 ∘ C. Non-homogeneous breakdown between the yield and flow stresses was found which, when coupled with thixotropy, helps identify the source of nutrient losses during tube feeding.