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At least 19 records

Source of Processable Vitrimer Viscosities: Swap Frequencies and Steric Factors

Vitrimers exhibit high, processable viscosities, where other polymers do not, and are among the most promising polymers for closed-loop material circularity. We sought to investigate the underlying chemical kinetic factors that result in high viscosities for vitrimers, which are crucial to designing vitrimers with tunable viscosity. To interrogate these factors, we achieved the first simulated predictions of real vitrimer viscosities, using a novel kinetic Monte Carlo molecular dynamics method, overcoming the time and length scale gaps to predict experimental bulk viscosities. The vitrimer architecture investigated is based on poly(dimethylsiloxane) chains and vinylogous urethane bond swaps. We probed the effects of the extent of free swapping groups, %F, the activation energy, E A , and the steric factor, ρ. The steric factor is related to the intrinsic reaction probability for molecules with sufficient energy. All three factors were found to be significant, but the role of ρ was found to be the biggest and also the most underappreciated. The results show that the inclusion of accurate ρ is of critical importance for viscosity predictions, with the evidence suggesting that the typical assumption of ρ = 1 is not valid for vitrimers and that, indeed, very low steric factors are present in bond-swap vitrimers such that values of ρ < 10 –10 may be typical. This greatly influences the bond exchange rates and, ultimately, the viscosities. Recognition of this result is necessary for the prediction of vitrimer viscosities from molecular simulations and to make vitrimers by design from molecular dynamics. We also investigated the effects that E A , ρ, and the number of free swapping groups have upon vitreous range temperatures, TV, with respect to achieving a specific viscosity (η V = 1 × 10 8 Pa·s), as well as for a commonly reported higher viscosity extrapolation (η V = 1 × 10 12 Pa·s). The evidence suggests that vitrimers may follow universal curves for E A vs T V , as a function of ρ. Finally, this study achieves the first of these comparisons of molecular simulations to experiments and reveals critical insights toward creating vitrimers by design, while providing a route for the prediction of T V from kinetic Monte Carlo molecular dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Intrinsic bulk viscosity of the one-component plasma

The intrinsic bulk viscosity of the one-component plasma (OCP) is computed and analyzed using equilibrium molecular dynamics simulations and the Green-Kubo formalism. It is found that bulk viscosity exhibits a maximum at Γ ≈ 1, corresponding to the condition that the average kinetic energy of particles equals the potential energy at the average interparticle spacing. The weakly coupled and strongly coupled limits are analyzed and used to construct a model that captures the full range of coupling strengths simulated: Γ ≈ 10 –2 –10 2 . Simulations are also run of the Yukawa one-component plasma (YOCP) in order to understand the impact of electron screening. It is found that electron screening leads to a smaller bulk viscosity due to a reduction in the excess heat capacity of the system. Bulk viscosity is shown to be at least an order of magnitude smaller than shear viscosity in both the OCP and YOCP. The generalized frequency-dependent bulk viscosity coefficient is also analyzed. This is found to exhibit a peak near twice the plasma frequency in strongly coupled conditions, which is associated with the oscillatory decay observed in the bulk viscosity autocorrelation function. As a result, the generalized shear and bulk viscosity coefficients are found to have a similar magnitude for ω ≳ 2⁢ω p at strongly coupled conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Distinct Gas-Particle Partitioning and Viscosity Characteristics of Secondary Organic Aerosols Derived from α-Pinene versus Ocimene

Secondary organic aerosols (SOA) have complex, multicomponent composition that controls particle viscosity and gas-particle partitioning, key factors to their atmospheric evolution. This study investigates the chemical composition, volatility and viscosity of SOA formed by ozonolysis of cyclic α-pinene (PSOA) and acyclic ocimene (OSOA) monoterpenes. Using Temperature-Programmed Desorption combined with Direct Analysis in Real-Time ionization and High-Resolution Mass Spectrometry, we determined the molecular composition and saturation mass concentration of individual SOA constituents. These data enabled gas-particle partitioning and viscosity estimates under varied atmospheric conditions. PSOA, composed of higher molecular weight and less oxidized species, shows higher condensability and viscosity under high total organic mass (tOM) loadings. Here, in contrast, OSOA, consisting of more oxidized, lower molecular weight species, exhibits greater sensitivity to tOM, with viscosity increasing significantly upon dilution. Poke-flow experiments support this trend, indicating that OSOA undergoes more dynamic compositional and phase changes during atmospheric aging. These observations reveal distinct dynamic trends in the atmospheric transformations and reactivity of SOA from cyclic and acyclic monoterpenes, with the latter showing greater compositional changes during aging that alter viscosity and diffusion. This highlights the importance of incorporating such dynamic transformations into atmospheric models to improve predictions of SOA atmospheric loadings, lifetimes, and impacts.

cyclic and acyclic monoterpenes

High-throughput small-angle X-ray scattering reveals effective structure factor transitions linked to high-concentration antibody viscosity

High-concentration monoclonal antibody (mAb) formulations are often constrained by elevated viscosity, largely driven by protein–protein interactions, which complicates manufacturing and limits subcutaneous delivery. Early viscosity risk assessment is essential during discovery, yet traditional measurements require large sample volumes, and lack high-throughput capability. Here, we develop a high-throughput small-angle X-ray scattering (SAXS) protocol to detect mAb self-association at dilute concentrations, enabling early predictive insights into high-concentration viscosity. Synchrotron SAXS measurements were conducted for 21 mAbs formulated in a histidine buffer at pH 6.0. An initial subset of 10 mAbs analyzed across 1–150 mg/mL revealed that effective structure factor transitions in the low-q region, indicative of interparticle interactions, consistently emerged below 25 mg/mL. Subsequently, 11 additional mAbs were analyzed at 1–25 mg/mL using automated liquid handling and flow cells to enable high-throughput screening. High-viscosity mAbs exhibited detectable low-q upturns at concentrations ≤10 mg/mL, whereas low-viscosity mAbs showed downturns. A classification criterion based on effective structure factor transitions accurately classified all high- and low-viscosity mAbs at 150 mg/mL, offering a scalable, sample-efficient alternative to conventional methods. These results extend recent findings on the concentration-dependent sensitivity of SAXS to short-range attractions, demonstrating that they can emerge at lower concentrations than previously reported. This study presents the most comprehensive and diverse SAXS dataset for mAbs reported to date within a single formulation, providing a valuable resource for developing and validating coarse-grained models that can more accurately capture intermolecular interactions governing high-concentration solution behavior, thereby enabling rational antibody engineering and improved developability.

36 MATERIALS SCIENCE

Bulk viscosity of nuclear matter with pions in the neutrino-trapped regime

Recent work has shown that a population of thermal pions could modify the equation of state and transport properties of hot and dense neutron-rich matter and introduce new reaction pathways to change the proton fraction. In this article we study their impact on the bulk viscosity of dense matter, focusing on the neutrino-trapped regime that would be realized in neutron star mergers and supernovae. We find that the presence of a thermal population of pions alters the bulk viscosity by modifying the EoS (via the susceptibilities) and by providing new reaction pathways to achieve beta equilibrium. In neutron star merger conditions, the bulk viscosity in neutrino-trapped npeμ matter (without pions) has its peak at temperatures of at most a couple MeV and is quite small at temperatures of tens of MeV. We find that thermal pions enhance the low-temperature peak of the bulk viscosity by a factor of a few and shift it to slightly lower temperatures. At higher temperatures, where the pion abundance is large but the bulk viscosity is traditionally small, pions can increase the bulk viscosity by an order of magnitude or more, although it is still orders of magnitude smaller than its peak value.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Impact of melt viscosity on filler dispersion in elastomeric nanocomposites

Compounding of commercial nanocomposites usually involves the addition of viscosity enhancers such as binder resins in ink jet inks, and paints. Contrary to this, plasticizers such as process oils are added to reduce the melt viscosity and ease processability of reinforced elastomers. Nanofillers such as silica and carbon black are typically added to reinforce rubber and enhance performance of automotive tire treads. Filler dispersion has traditionally been qualitatively (indirectly) assessed by measuring the properties of reinforced elastomers. While dispersion can be quantified by examining filler agglomeration through surface roughness measurements and microscopy, the size-scale dependence for these hierarchical fillers has usually been ignored. Here, we have recently devised a method to quantify nano-scale dispersion of fillers using Ultra small-angle X-ray scattering (USAXS) techniques. This method is advantageous since it directly links the controllable processing/compounding parameters such as the mixing speed, mixer geometry, residence time (or mixing duration), melt density, flow gap distance, and melt viscosity to nano-scale dispersion. While our previous studies have explored the impact of different processing parameters, this study specifically investigates the impact of melt viscosity on nano-scale filler dispersion in elastomer compounds. Commercially available polybutadienes with different Mooney viscosities were used in conjunction with different grades and amounts of process oils to modify the melt viscosity.

Carbon black

A theoretical/computational framework to measure SiO2 and MgO viscosity at high pressure

The convection of the mantle of Earth and super-Earths is important for many terrestrial phenomena, from plate tectonics to outgassing. Rheological properties, such as viscosity, regulate the transport of thermal energy and mass. However, the viscosity of mantle-relevant materials, such as MgO, at relevant pressures (>120 GPa) are not well constrained. The objective of this work was to develop a computational platform to simulate novel experiments aiming to measure the viscosity of MgO at high pressures. Experiments performed by our collaborators at Johns Hopkins University and Lawrence Livermore National Laboratory use the OMEGA EP laser facility to shock a corrugated MgO interface to 170 GPa, with resulting velocity evolution governed by the viscous Richtmyer-Meshkov instability. We used an in-house hydrocode to simulate this process and thus provide a bound on viscosity by comparing our simulations results to these experiments, as well as to examine the physical processes at play. We simulated the experiments with different values of MgO viscosity (from inviscid to 10,000 Pa∙s) while taking into account the unsteady laser pulse, the material's equation of state, and the rate-dependent constitutive relation for MgO, and the materials' equations of state. Our results suggest that MgO at these conditions has a viscosity within an order of magnitude of 5000 Pa∙s.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

A spline-based method to obtain spatially dependent viscosity in confined flows

Coupling chemical physics to continuum theories is a critical step to understanding multi-scale phenomena. This paper will connect non-equilibrium molecular dynamics simulations to a continuum-based Navier-Stokes equation that has relaxed the assumption of spatial uniformity in viscosity. Using a form for viscosity based on spline interpolation, viscosity as a function of position is obtained from the least squares fit of the velocity profile measured from molecular simulations of flow in a nanochannel. Viscosity can vary widely, particularly near the channel boundaries, indicating that uniform viscosity is no longer appropriate. Variations of the viscosity near the channel surfaces imply that considering solution and surface chemistry could be necessary to rigorously understand molecular-scale flows in nanochannels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Effect of artificial viscosity on shocked particle-laden flows for staggered grid Lagrangian methods

Abstract Shocked particle-laden flows are important to many natural and industrial processes. When simulating these systems, artificial viscosity is often required to prevent numerical artifacts, such as ringing, from arising in the pressure and density fields. The linear and quadratic coefficients of the artificial viscosity determine the amount of smoothing that occurs in these fields. For particle-laden flows, however, many of the fluid–particle interaction forces, for example, the pressure gradient force and unsteady forces, depend on gradients in the fluid fields. Furthermore, while the shock passes over a particle, these forces can be more dominant than drag. This means that the artificial viscosity coefficients affect how a particle and fluid interact when simulating shocked particle systems. Here this effect is investigated for isolated particles and for a particle curtain using a staggered grid Lagrangian approach. The artificial viscosity coefficients have a significant impact on the maximum force that a fluid imparts to a particle, which is important for determining whether a particle will break up in response to the shock. Furthermore, it is found that the density ratio between the particle and the fluid is important in determining whether the artificial viscosity coefficients have a significant impact on the particle’s motion.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC

Revisiting the validity of eddy viscosity models for predicting airflow over water waves

In this study, we revisit the validity of eddy viscosity models for predicting wave-induced airflow disturbances over ocean surface waves. We first derive a turbulence curvilinear model for the phase-averaged Navier–Stokes equations, extending the work of Cao, Deng & Shen (2020 J. Fluid Mech. 901, A27), by incorporating turbulence stress terms previously neglected in the linearised viscous curvilinear model. To verify our formulation, we perform a priori tests by numerically solving the model using mean wind and turbulence stress profiles from large-eddy simulations (LES) of airflow over waves across various wave ages. Results show that including turbulence stress terms improves wave-induced airflow predictions compared with the previous viscous curvilinear model. We further show that using a standard mixing-length eddy viscosity yields inaccurate predictions at certain wave ages, as it fails to capture wave-induced turbulence, which fundamentally differs from mean shear-driven turbulence. The LES data show that accurate representations of wave-induced stresses require a complex-valued eddy viscosity. The maximum magnitude of this eddy viscosity scales as ∼𝑢 𝜏 ⁢𝜁 𝑖𝑛𝑛𝑒𝑟 , where 𝑢 𝜏 is the friction velocity and 𝜁 𝑖𝑛𝑛𝑒𝑟 is the inner-layer thickness, the height at which the eddy-turnover time matches the wave advection time scale. This scaling aligns with the prediction by Belcher & Hunt (1993 J. Fluid Mech. 251, 109–148). Overall, the findings demonstrate that traditional eddy viscosity models are inadequate for capturing wave-induced turbulence. More sophisticated turbulence models are essential for the accurate prediction of airflow disturbances and form drag in wind–wave interaction models.

16 TIDAL AND WAVE POWER

Taking control of compressible modes: bulk viscosity and the turbulent dynamo

Many polyatomic astrophysical plasmas are compressible and out of chemical and thermal equilibrium, introducing a bulk viscosity into the plasma via the internal degrees of freedom of the molecular composition, directly impacting the decay of compressible modes, $\mathrm{{\boldsymbol {\mathit {v}}}}_{\parallel }(\boldsymbol {k})$. This is especially important for small-scale, turbulent dynamo processes in the interstellar medium (ISM), which are known to be sensitive to the effects of compression. To control the viscous properties of $\mathrm{{\boldsymbol {\mathit {v}}}}_{\parallel }(\boldsymbol {k})$, we perform trans-sonic, visco-resistive dynamo simulations with additional bulk viscosity $\nu _{\text{bulk}}$, deriving a new $\nu _{\text{bulk}}$ Reynolds number $\text{Re}_{\text{bulk}}$, and viscous Prandtl number $\text{P}\nu \equiv \text{Re}_{\text{bulk}}/ \text{Re}_{\text{shear}}$, where $\text{Re}_{\text{shear}}$ is the shear viscosity Reynolds number. We derive a framework for decomposing $E_{\rm mag}$ growth rates into incompressible and compressible terms via orthogonal tensor decompositions of $\boldsymbol {\nabla }\otimes \mathrm{{\boldsymbol {\mathit {v}}}}$, where $\mathrm{{\boldsymbol {\mathit {v}}}}$ is the fluid velocity. We find that $\mathrm{{\boldsymbol {\mathit {v}}}}_{\parallel }(\boldsymbol {k})$ play a dual role, growing and decaying $E_{\rm mag}$, and that field-line stretching is the main driver of growth, even in compressible dynamos. In the absence of $\nu _{\text{bulk}}$ ($\text{P}\nu \rightarrow \infty$), $\mathrm{{\boldsymbol {\mathit {v}}}}_{\parallel }(\boldsymbol {k})$ pile up on small-scales, creating a spectral bottleneck, which disappears for $\text{P}\nu \approx 1$. As $\text{P}\nu$ decreases, $\mathrm{{\boldsymbol {\mathit {v}}}}_{\parallel }(\boldsymbol {k})$ are dissipated at increasingly larger scales, in turn suppressing incompressible modes through a coupling between high-k modes. We emphasize the importance of further understanding the role of $\nu _{\text{bulk}}$ in compressible astrophysical plasmas, which we estimate could be as strong as the shear viscosity in the cold ISM, and highlight that compressible direct numerical simulations without bulk viscosity have unresolved compressible mode dissipation scales.

MHD

Shear viscosity from perturbative quantum chromodynamics to the hadron resonance gas at finite baryon, strangeness, and electric charge densities

Through model-to-data comparisons from heavy-ion collisions, it has been shown that the quark gluon plasma has an extremely small shear viscosity at vanishing densities. At large baryon densities, significantly less is known about the nature of the shear viscosity from quantum chromodynamics (QCD). Within heavy-ion collisions, there are three conserved charges: baryon number (B), strangeness (S), and electric charge (Q). Here we calculate the shear viscosity in two limits using perturbative QCD (pQCD) and an excluded-volume hadron resonance gas at finite BSQ densities. We then develop a framework that interpolates between these two limits such that shear viscosity is possible to calculate across a wide range of finite BSQ densities. We find that the pQCD and hadron resonance gas calculations have different BSQ density dependencies such that a rather nontrivial shear viscosity appears at finite densities.

Phenomenology

Lattice-scale variations in viscosity are correlated with solution structure at mineral-water interfaces

At solid-liquid interfaces, the viscosity increases markedly from the bulk due to the collective interactions of ions and water molecules, influencing phenomena relevant to nanofluidics, colloidal dynamics, and electrochemistry. Here, in this study, we investigated dissipative forces at the boehmite-water interface using 3D atomic force microscopy. We observed an increase in interfacial solution viscosity, η, by 10-100-fold as the nanoprobe approached the surface in normal direction, with up to four oscillatory features showing average peaks of η/η bulk = 44-71. Moreover, the viscosity showed sub-nanometer variations within 0.5 nm from the interface, templated by the underlying crystal lattice and correlated with the interfacial solution structure. Beyond a near-wall region of approximately 1.2 nm, the dissipative response was comparable to that in bulk solution. Molecular dynamics simulations, along with statistical mechanical analyses, provided details on hydrodynamic structures near the interface. Specifically, the lattice-dependent dissipative responses are correlated with extensive hydrogen bonding by interfacial water molecules, which increased friction, particularly along the [001] direction. These results demonstrate how solution viscosity at mineral-water interfaces is anisotropic and correlated with the local solution structure, providing insights into the dynamics of nanocrystal attachment.

Viscosity

Stockmayer fluid simulations for viscosity and glass transition temperature of ionic liquids

We develop a Stockmayer fluid model for molecular dynamics simulations of ionic liquids that captures molecular polarization, ionic conductivity, viscosity, and glass transition temperature, using ethylammonium nitrate (EAN) as an example. The ions in EAN are treated as spheres interacting via the Lennard-Jones potential with an embedded point charge and a permanent dipole moment. We show that our simulation results for EAN are consistent with experimental data and then explore the effects of the molecular parameters on the viscosity of ionic liquids. Our results indicate that viscosity monotonically increases with ionic charge and dipole moment but non-monotonically changes with ionic diameter (or molar volume). This non-monotonic trend arises from the competition among the electrostatic interactions, molecular packing, and size asymmetry between the cation and anion. In conclusion, our model also shows that long-lived ion pairs result in higher viscosities.

Coarse-grained simulations

Effect of Oil Viscosity and Impact of Ionic Liquid Additive on Electrically Induced Pitting in Rolling Contact

Electrically induced bearing damage (EIBD) is a growing concern in electric drivetrains, where electrical discharge currents generate localized pitting that accelerates wear and premature failure. While ionic liquids (ILs) have shown promise as lubricant additives due to their natural physical adsorption, strong capabilities of tribofilm formation, and high molecular tunability, their role in mitigating EIBD is little known. This gap is especially evident because lubricant viscosity and film thickness affect discharge behavior, and additive performance in these regimes has not been well explored. In this study, tribological tests were performed using a ball-on-disk pure rolling-contact system under an applied voltage on polyalphaolefin oils of three viscosities (4, 10, and 150 cSt measured at 100 °C), with and without the addition of a phosphonium-phosphate IL. Surface damage was analyzed using scanning electron microscopy (SEM) and stylus profilometry. Damage quantification was based on pit morphology analysis of SEM images. The results provide new insights into how oil viscosity governs the discharge behavior and how an IL additive could influence the pit formation. While viscosity seems to play a significant role, an IL additive shows potential to reduce EIBD and deserves further study.

electrically induced bearing damage (EIBD)

Reference Correlations for the Density and Viscosity of Molten Alkali and Alkaline Earth Fluoride Salts

While there is a significant body of literature pertaining to thermophysical property measurements of molten salts, there is often a wide degree of variability among independent measurements of the same compounds. As such, the scientific community benefits greatly from an unbiased, independent assessment of duplicate datasets, so that reference correlations which describe these thermophysical properties as functions of temperature can be determined and then commonly used by researchers, scientists, and engineers. With regard to molten fluoride compounds, a significant time has elapsed since density and viscosity reference correlations have been determined; Janz conducted the most recent effort, in 1988, to provide reference correlations for the densities and viscosities of molten fluoride compounds via the National Standard Reference Data System coordinated by the National Bureau of Standards. Since then, new data have been published for molten fluoride compounds, and a new precedent has surfaced for putting forth reference correlations that involve fitting to multiple primary datasets. In this work, reference correlations are put forth for molten alkali and alkaline earth fluoride compounds in an effort to provide updated, improved correlations for general use. For molten alkali fluoride densities, estimated uncertainties with a 95% confidence interval are summarized as follows: LiF (0.63%), NaF (0.48%), KF (0.76%), RbF (0.93%), and CsF (0.75%). For molten alkaline earth fluoride densities, an estimated uncertainty was not able to be quantified for BeF 2 because of limited data; however, estimated uncertainties with a 95% confidence interval are summarized as follows for the remaining alkaline earth fluorides: MgF 2 (1.5%), CaF 2 (0.92%), SrF 2 (1.6%), and BaF 2 (0.23%). For molten alkali fluoride viscosities, uncertainty was not able to be quantified for RbF and CsF because of limited data; however, estimated uncertainties with a 95% confidence interval are summarized as follows for the remaining alkali fluorides: LiF (4.4%), NaF (3.0%), and KF (4.0%). For molten alkaline earth fluoride viscosities, limited consistent data resulted in the recommendation of single datasets (from literature) that are deemed to be the most trustworthy based on the quality of the underlying experimental studies.

Birri, A. [Oak Ridge National Laboratory (ORNL), O

Investigation of resonant layer response in electron viscosity regime

We present a supplementary study of previous work in Waybright and Park [Phys. Plasmas 31, 022502 (2024)] which demonstrates a substantial effect of electron viscosity on the resonant layer response to non-axisymmetric magnetic perturbations. A main refinement is to include a curl element of electron viscosity in the generalized Ohm's law. The refinement reveals a resonant layer response in the electron viscosity regime corresponding to slowly rotating and highly viscous plasmas.

Asymptotic analysis

Sedimentation and shear-induced dynamics of spheroids in fluids with spatial viscosity variations

A generalized reciprocal theorem is used to relate the force and torque induced on a particle in an inertia-less fluid with small variation in viscosity to integrals involving Stokes flow fields and the spatial dependence of viscosity. These resistivity expressions are analytically evaluated using spheroidal harmonics and then used to obtain the mobility of the spheroid during sedimentation, and in linear flows, of a fluid with linear viscosity stratification. The coupling between the rotational and translational motion induced by stratification rotates the spheroid’s centerline, creating a variety of rotational and translational dynamics dependent upon the particle’s aspect ratio, κ, and the component of the stratification unit vector in the gravity direction, d g . Spheroids with 0.55 ⪅ κ ⪅ 2.0 exhibit the largest variety of settling behaviors. Interestingly, this range covers most microplastics and typical microorganisms. One of the modes include a stable orientation dependent only on κ and d g , but independent of initial orientation, thus allowing for the potential control of settling angles and sedimentation rates. In a simple shear flow, cross-streamline migration occurs due to the stratification-induced force generated on the particle. Similarly, a particle no longer stays at the stagnation point of a uniaxial extensional flow. While fully analytical results are obtained for spheroids, numerical simulations provide a source of validation. These simulations also provide additional insights into the stratification-induced force- and torque-producing mechanisms through the stratification-induced stress, which is not accessed in the reciprocal theorem-based analytical calculations.

Geophysical and Geological Flows: Stratified flows