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We propose and study methods to improve tactile intuition for linear viscoelastic fluids. This includes (i) Pipkin mapping with amplitude based on stress rather than strain or strain-rate to map perception to rheological test conditions; and (ii) data reduction of linear viscoelastic functions to generate multi-dimensional Ashby-style cross-property plots. Two model materials are used, specifically chosen to be easily accessible and safe to handle, with variable elastic, viscous, and relaxation time distributions. First, a commercially available polymer melt known as physical therapy putty, reminiscent of Silly Putty, designed for a range of user experiences (extra-soft to extra-firm). Second, a transiently cross-linked aqueous polymer solution (Polyvinyl alcohol-Sodium Tetraborate, PVA-Borax). Readers are encouraged to procure or produce the samples themselves to build intuition. The methods studied here reduce the complexity of the function-valued viscoelastic data, identifying what key features we sense and see when handling these materials, and provide a framework for tactile intuition, material selection, and material design for linear viscoelastic fluids generally.

We all instinctively poke, bounce, scoop, and observe materials to understand rheological properties quickly. Yet, these observations are rarely analyzed quantitatively. To address this, here we introduce the paradigm of protorheology: approximate quantitative inference from simple observations. Several case studies demonstrate how protorheology is an inclusive entry to rheology for a broad range of practitioners and strengthens the confidence and interpretation of accurate laboratory measurements. We survey a range of creative tests according to which rheological phenomenon is revealed. Some new working equations are derived, and all working equations are summarized for convenient reference and comparison across different methods. This establishes a framework to enable increased use of photos, videos, and quantitative inference and to support the increasing interest in digital image analysis, inverse methods, and high-throughput characterization being applied to rheological properties. [ABSTRACT FROM AUTHOR]

Thixotropy, antithixotropy, and viscoelasticity are three types of time-dependent dynamics that involve fundamentally different underlying physical processes. Here, we show that the three dynamics exhibit different signatures in hysteresis by examining the fingerprints of the simplest thixotropic kinetic model, a new antithixotropic model that we introduce here, and the Giesekus model. We start by showing that a consistent protocol to generate hysteresis loops is a discrete shear-rate controlled ramp that begins and ends at high shear rates, rather than at low shear rates. Using this protocol, we identify two distinguishing features in the resulting stress versus shear rate loops. The first is the direction of the hysteresis loops: clockwise for thixotropy, but counterclockwise for viscoelasticity and antithixotropy. A second feature is achieved at high ramping rates where all responses lose hysteresis: the viscoelastic response shows a stress plateau at low shear rates due to lack of stress relaxation, whereas the thixotropic and antithixotropic responses are purely viscous with minimal shear thinning or thickening. We establish further evidence for these signatures by experimentally measuring the hysteresis of Laponite suspensions, carbon black suspensions, and poly(ethylene oxide) solutions, each representing a historically accepted example of each class of material behavior. The signatures measured in experiments are consistent with those predicted by the three models. This study reveals different fingerprints in hysteresis loops associated with thixotropy, antithixotropy, and viscoelasticity, which may be helpful in distinguishing the three time-dependent responses. [ABSTRACT FROM AUTHOR]

Increasing redox‐active species concentrations can improve viability for organic redox flow batteries by enabling higher energy densities, but the required concentrated solutions can become viscous and less conductive, leading to inefficient electrochemical cycling and low material utilization at higher current densities. To better understand these tradeoffs in a model system, we study a highly soluble and stable redox‐active couple, N‐(2‐(2‐methoxyethoxy)ethyl)phenothiazine (MEEPT), and its bis(trifluoromethanesulfonyl)imide radical cation salt (MEEPT‐TFSI). We measure the physicochemical properties of electrolytes containing 0.2–1 M active species and connect these to symmetric cell cycling behavior, achieving robust cycling performance. Specifically, for a 1 M electrolyte concentration, we demonstrate 94% materials utilization, 89% capacity retention, and 99.8% average coulombic efficiency over 435 h (100 full cycles). This demonstration helps to establish potential for high‐performing, concentrated nonaqueous electrolytes and highlights possible failure modes in such systems. [ABSTRACT FROM AUTHOR]

Understanding the physical and chemical processes occurring in concentrated electrolyte solutions is required to achieve redox flow batteries with high energy density. Highly concentrated electrolyte solutions are often studied in which collective crowded interactions between molecules and ions become predominant. Herein, experimental and computational methods were used to examine non-aqueous electrolyte solutions in two different states of charge as a function of redoxmer concentration. As the latter increases and the ionic association strengthens, the electric conductivity passes through a maximum and the solution increasingly gels, which is seen through a rapid non-linear increase in viscosity. We establish that the structural rigidity of ionic networks is closely connected with this loss of fluidity and show that charging generally yields softer ionic assemblies with weaker attractive forces and improved dynamical properties. [ABSTRACT FROM AUTHOR]

We report a detailed experimental study of peculiar thixotropic dynamics of carbon black (CB, Vulcan XC-72) suspensions in mineral oil, specifically the observation of sequential stress increase then decrease at a fixed shear rate in a step-down test. We verify that such dynamics, though peculiar, come from a true material response rather than experimental artifacts. We also reveal how this long-time stress decay is associated with antithixotropic structural change rather than viscoelastic stress relaxation by using orthogonal superposition (OSP) rheometry to probe viscoelastic moduli during the step-down tests. The orthogonal storage and loss moduli are present, showing this two-timescale recovery then decay response, which demonstrates that this response is antithixotropic, and it involves shear-induced structuring. We further show a mechanical anisotropy in the CB suspension under shear using OSP. Based on the rheological results, a microstructural schematic is proposed, considering qualitatively thixotropic structure build-up, antithixotropic densification, and anisotropic structure evolution. Our observation for these CB suspensions is outside the standard paradigm of thixotropic structure-parameter models, and the elastic response provides us with new insight into the transient dynamics of CB suspensions. [ABSTRACT FROM AUTHOR]

There is no universal model for thixotropy, and comparing thixotropic effects between different fluids is a subtle yet challenging problem. We introduce a generalized (model-insensitive) framework for comparing thixotropic properties based on thixotropic spectra. A superposition of exponential stress modes distributed over thixotropic time scales is used to quantify buildup and breakdown times and mode strengths in response to step-change input. This mathematical framework is tested with several experimental step-shear rate data on colloidal suspensions. Low-dimensional metrics based on moments of the distribution reveal characteristic average thixotropic properties, which are visualized on Ashby-style diagrams. This method outlines a framework for describing thixotropy across a diverse range of microstructures, supporting scientific studies as well as material selection for engineering design applications. [ABSTRACT FROM AUTHOR]

The ability to manufacture highly intricate designs is one of the key advantages of 3D printing. Achieving high dimensional accuracy requires precise, often time‐consuming calibration of the process parameters. Computerized feedback control systems for 3D printing enable sensing and real‐time adaptation and optimization of these parameters at every stage of the print, but multiple challenges remain with sensor embedment and measurement accuracy. In contrast to these active control approaches, here, the authors harness frontal polymerization (FP) to rapidly cure extruded filament in tandem with the printing process. A temperature gradient present along the filament, which is dependent on the printing parameters, can impose control over this exothermic reaction. Experiments and theory reveal a self‐regulative mechanism between filament temperature and cure kinetics that allows the frontal cure speed to autonomously match the print speed. This self‐regulative printing process rapidly adapts to changes in print speed and environmental conditions to produce complex, high‐fidelity structures and freestanding architectures spanning up to 100 mm, greatly expanding the capabilities of direct ink writing (DIW). [ABSTRACT FROM AUTHOR]