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At least 19 records

Use of a Lignin-Based Admixture for Tailoring the Rheological Properties of Mortars for 3D Printing: Preprint

Efforts toward decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a more reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of polycarboxylate ether admixtures with a smaller carbon footprint. The present study examines the use of lignin-based water-reducing admixture in cement pastes and mortar mixtures for 3D printing. The experimental program explores the use of different dosages of lignin-based admixture to produce 3D-printed samples with appropriate extrudability and buildability. The rheological characterization was performed to determine the flow curve of various mixtures. Finally, the heat of hydration of cement pastes was monitored via isothermal calorimetry to assess the impact of lignin-based admixtures on the hydration process of cement. The results of this study indicate that the use of biomass by-products, such as lignin-based admixtures have great potential to effectively control the fresh-state properties of cement-based materials.

bio-based admixtures

Rheological transition in mantle convection with a composite temperature-dependent, non-Newtonian and Newtonian rheology

Numerical simulations of mantle convection with a composite temperature-dependent, Newtonian and non-Newtonian creep law have revealed a transition in the dominant creep mechanism with the increasing vigour of convection. Newtonian creep is found to dominate in the low Rayleigh number regime. With sufficiently high effective Rayleigh number, the overall creep mechanism in the convective flow becomes non-Newtonian. The transitional Rayleigh number increases strongly with the activation energy. These results would suggest a scenario that in the early epochs of Earth the flow in the mantle would have been governed by non-Newtonian rheology and would have exhibited both strong spatial and temporal fluctuations. With time the flow mechanism would behave like a Newtonian fluid and would have a different time-dependent character. In time-dependent Newtonian-dominated flows there are still localized features with distinctly non-Newtonian character. Our analysis of the relative contributions to the lateral viscosity field supports the idea that the inference of the nature of lateral viscosity heterogeneities by seismic tomography may be strongly contaminated by the dominant non-Newtonian contributions to the total lateral viscosity field.

Van Den Berg, Arie P.

Extensional Rheology Experiment Developed to Investigate the Rheology of Dilute Polymer Solutions in Microgravity

A fundamental characteristic of fluid is viscosity; that is, the fluid resists forces that cause it to flow. This characteristic, or parameter, is used by manufacturers and end-users to describe the physical properties of a specific material so that they know what to expect when a material, such as a polymer, is processed through an extruder, a film blower, or a fiber-spinning apparatus. Normally, researchers will report a shear viscosity that depends on the rate of an imposed shearing flow. Although this type of characterization is sufficient for some processes, simple shearing experiments do not provide a complete picture of what a processor may expect for all materials. Extensional stretching flows are common in many polymer-processing operations such as extrusion, blow molding, and fiber spinning. Therefore, knowledge of the complete rheological (ability to flow and be deformed) properties of the polymeric fluid being processed is required to accurately predict and account for the flow behavior. In addition, if numerical simulations are ever able to serve as a priori design tools for optimizing polymer processing operations such as those described above, an accurate knowledge of the extensional viscosity of a polymer system and its variation with temperature, concentration, molecular weight, and strain rate is critical.

Logsdon, Kirk A.

Shear History Extensional Rheology Experiment II (SHERE II) Microgravity Rheology with Non-Newtonian Polymeric Fluids

The primary objective of SHERE II is to study the effect of torsional preshear on the subsequent extensional behavior of filled viscoelastic suspensions. Microgravity environment eliminates gravitational sagging that makes Earth-based experiments of extensional rheology challenging. Experiments may serve as an idealized model system to study the properties of lunar regolith-polymeric binder based construction materials. Filled polymeric suspensions are ubiquitous in foods, cosmetics, detergents, biomedical materials, etc.

Jaishankar, Aditya

Methodology to determine printability criteria of highly concentrated pastes through rheological characterization

Material extrusion is an additive manufacturing technique that enables the creation of reproducible and complex hardware by depositing a viscous, shear-thinning ink onto a substrate in a custom-pattern via extrusion through a syringe. Here, the ability of an ink to be extruded onto a substrate in many layers, and maintain the desired shape is what defines the printability. Printability is often investigated by formulating, printing, and postmortem analysis of final parts in an iterative manner. Investigations of printability through rheological characterization have often been concerned with inks that straddle the line between printable and too thin, leaving out an entire class of inks that are highly-filled pastes, where extrudability is the limiting factor. Highly-filled pastes continue to pose issues for researchers as the effect of filler morphology, size, loading, and packing fraction on the ink rheology and corresponding printability is not understood. While traditional rheological characterizations may be useful for some inks, we show that protocols utilizing steady-shear, or large-amplitude oscillatory shear are difficult and unreliable for highly-filled pastes. Through transient rheology paired with real-time images we show that each traditional protocol produces inhomogeneous deformations that violate the assumptions that underly common rheological definitions. Instead, we demonstrate metrics measured with small-amplitude oscillatory shear that are correlated to the printability of various ink formulations ranging in loading. The rheological measures that accurately predict the printability of the inks are the axial stress measured at small amplitudes, and the critical stress amplitude above which rheological characterizations become impossible. In addition, we estimate the maximum packing fraction for each filler, based on the exponent common to hard sphere models, and show that the printability of each ink can be predicted by the ratio of the packing fraction to the theoretical maximum. We show how small-amplitude oscillatory shear allows users to develop printability criteria for any ink to enhance the workflow in the development of new inks, increase the performance of material extrusion printing, and improve the stability of printed parts, with less wasted time and materials.

36 MATERIALS SCIENCE

A comparison of calculated and measured rheological properties of crystallising lavas in the field and in the laboratory

Models of most magmatic processes, including realistic models of planetary lava flows require accurate data on the rheological properties of magma. Previous studies suggest that field and laboratory rheological properties of Hawaiian lavas can be calculated from their physico-chemical properties using a non-Newtonian rheology model. The present study uses new measurements of the rheological properties of crystallizing lavas to show that this is also true for lavas from Mount Etna. Rheological measurements on quenched Etna basalts were made in a specially designed furnace using a Haake Rotovisco viscometer attached to a spindle which has been designed to eliminate slippage at the melt-spindle interface. Using this spindle, we have made measurements at lower temperatures than other workers in this field. From these measurements, Mount Etna lavas are Newtonian at temperatures above 1120 C and they are thixotropic pseudoplastic fluids with a yield strength at lower temperatures. The close agreement between calculated and measured rheology over the temperature range 1084 - 1125 C support the use of the non-Newtonian rheology model in future modeling of planetary lava flows.

Pinkerton, Harry

Insights into Preceramic Polymer-Based Additive Manufacturing Inks via Rheological and Scattering Studies of Preceramic Polymer-Grafted Nanoparticles Suspended in Polycarbosilane

Preceramic polymers (PCPs) offer advantages in producing ceramics due to their processability and ability to tailor the final chemistry of the produced material. However, challenges such as volumetric shrinkage and mass loss during pyrolysis often result in polymer-derived ceramics containing pores and cracks. PCP-grafted ceramic nanoparticles (PCPGNPs) have been proposed and studied as a route to mitigate the shrinkage issues associated with neat PCPs. Prior studies on PCPGNPs have principally focused on the synthesis and characterization of neat materials. Dispersing PCPGNPs in commercial preceramic polymer is another attractive, but underexplored, route to control the rheological and char yield properties of PCP systems. In this work, a systematic rheological study of commercial PCP (SMP-877) and PCPGNP (silica with poly(1,1-dimethylpropylsilane) corona) mixtures was executed to develop design rules for the processing of such systems. A rheological study demonstrated the effect of increasing particle concentration on network formation with percolation occurring between 50 and 60 wt %. Samples above the percolation threshold exhibited higher viscosities and rapid shear thinning thus demonstrating their direct-write printability. X-ray photon correlation spectroscopy (XPCS) corroborated the rheology and showed two diffusive modes when the material was above percolation. Mixtures of PCPGNPs and SMP-877 had synergistically higher char yields upon thermal treatment and pyrolysis. XPCS and rheological measurements during thermal treatment identified thermal jamming of the polymer grafts as a key factor in improving the char yield. In conclusion, with the insights gained here, we expect these mixed systems to provide attractive feedstocks for polymer-derived ceramics, with proof-of-principal application as feedstocks for direct ink write (DIW) additive manufacturing.

36 MATERIALS SCIENCE

Rheological Properties of Enzymatically Hydrolyzed Corn Stover Pretreated via Deacetylation and Mechanical Refining

Lignocellulosic biomass is a feedstock for fuels and chemicals that does not compete with food resources and has less contaminants than refuse-derived biomass feedstocks. To convert lignocellulosics to biofuels or value-added products, multiple processing steps are typically necessary. One method of producing biofuels from lignocellulosic biomass utilizes a deacetylation and mechanical refining pretreatment and an enzymatic hydrolysis reaction to produce fermentable sugars from cellulose and hemicellulose. The rheological properties of biomass, such as yield stress and plastic viscosity, change during enzymatic hydrolysis and alter the energy requirements for pumping and mixing, an important consideration for the design of processing equipment. The dynamic changes in rheological properties that occur in a corn stover feedstock undergoing enzymatic hydrolysis are characterized in this work, and the influence on pressure losses in piping systems is estimated. Two rheometer geometries were fabricated with stereolithography 3D printing to reduce wall slip and sample ejection. The slurries have complex rheological behaviors that include shear-thinning behavior. Shear stress ramps were performed on samples at 20 and 50 degrees C using the custom geometries, and the Herschel-Bulkley model was fit to the data. The dynamic nature of the rheological properties is correlated with changes in the average fiber length at various extents of reaction, and the influence of solids concentration on the observed rheology and piping pressure losses is discussed.

09 BIOMASS FUELS

Constraints on short-term mantle rheology from the J2 observation and the dispersion of the 18.6 y tidal Love number

Information derived from data recently acquired from the LAGEOS satellite is used to place some constraints on the rheological parameters of short-term mantle rheology. The validity of Lambeck and Nakiboglu's (1983) rheological model is assessed by formally developing an expression for the transformed shear modulus using a truncated retardation spectrum. This analytical formula is used to show that the parameters of the above mentioned model are not consistent at all with the amount of anelastic dispersion expected in the Chandler wobble and with the attenuation of seismic normal modes. The feasibility of a standard linear solid (SLS) rheology operating over intermediate timescales between 1 and 100 yr is investigated to determine whether the tidal dispersion at 18.6 yr can be explained by this model. An attempt is made to place some constraints on the parameters of the SLS model and the nature of short-term mantle rheology for timescales of less than 100 yr is discussed.

Sabadini, R.

Modeling of periodic great earthquakes on the San Andreas fault: Effects of nonlinear crustal rheology

We analyze the cycle of great earthquakes along the San Andreas fault with a finite element numerical model of deformation in a crust with a nonlinear viscoelastic rheology. The viscous component of deformation has an effective viscosity that depends exponentially on the inverse absolute temperature and nonlinearity on the shear stress; the elastic deformation is linear. Crustal thickness and temperature are constrained by seismic and heat flow data for California. The models are for anti plane strain in a 25-km-thick crustal layer having a very long, vertical strike-slip fault; the crustal block extends 250 km to either side of the fault. During the earthquake cycle that lasts 160 years, a constant plate velocity v(sub p)/2 = 17.5 mm yr is applied to the base of the crust and to the vertical end of the crustal block 250 km away from the fault. The upper half of the fault is locked during the interseismic period, while its lower half slips at the constant plate velocity. The locked part of the fault is moved abruptly 2.8 m every 160 years to simulate great earthquakes. The results are sensitive to crustal rheology. Models with quartzite-like rheology display profound transient stages in the velocity, displacement, and stress fields. The predicted transient zone extends about 3-4 times the crustal thickness on each side of the fault, significantly wider than the zone of deformation in elastic models. Models with diabase-like rheology behave similarly to elastic models and exhibit no transient stages. The model predictions are compared with geodetic observations of fault-parallel velocities in northern and central California and local rates of shear strain along the San Andreas fault. The observations are best fit by models which are 10-100 times less viscous than a quartzite-like rheology. Since the lower crust in California is composed of intermediate to mafic rocks, the present result suggests that the in situ viscosity of the crustal rock is orders of magnitude less the rock viscosity determined in the laboratory.

Reches, Ze'ev

Rheology of lignin and lignin-based solutions, dispersions, gels, polymer blends, and melts

Lignin is an abundant resource that finds application in energy and sustainable materials development. In addition to the utilization of lignin in three-dimensional (3D) printing and hydrogel production, recent studies have reported the use of lignin as a liquid fuel additive. The characterization of the rheological properties of lignin and its derivatives is a dynamic and evolving field, underpinned by advances in experimental, analytical, and modeling techniques. Here, this review provides a comprehensive overview of the recent progress in the study of lignin rheology, highlighting the interplay between structure, modification, and flow behavior in lignin-based solutions, dispersions, gels, polymer blends, and melts. A specific highlight of this review is how lignin concentration affects the rheological properties of lignin-based solutions and dispersions. Furthermore, the effect of lignin type on the properties of 3D-printed lignin-based composites is discussed. For polymer systems, this review discussed lignin-in-polymer solutions separately from lignin-filled polymer systems. Finally, challenges and perspectives on lignin rheology are presented.

Dispersions

The role of a pressure-dependent rheology in the dynamics of mantle circulation

A thermomechanical model for upper mantle convection was constructed such that the thickness and the structure of the lithosphere are determined self consistently by the heat transported by convection. In this study of the interaction between the lithosphere and upper mantle, strongly temperature and pressure dependent rheologies for both Newtonian and non-Newtonian creep mechanisms are employed. For a strictly temperature dependent rheology an insignificant amount of heat, less than 12.5 mW/sq m, can be transported convectively for an interior viscosity, 0(10 sup 21 Pas), compatible with post glacial rebound. On the other hand, for similar values of the interior viscosity, steady heat fluxes between 20 and 40 mW/sq m are produced by introducing pressure dependence into the rheology. For the temperature and pressure dependent flow law the horizontally averaged interior temperature displays very little variation with the amount of heat evacuated, once all of the rheological parameters are fixed. This finding may have important ramifications for parameterized convection.

Yuen, D. A.

Convection in Ice I with Composite Newtonian/Non-Newtonian Rheology: Application to the Icy Galilean Satellites

Ice I exhibits a complex rheology at temperature and pressure conditions appropriate for the interiors of the outer ice I shells of Europa, Ganymede, and Callisto. We use numerical methods to determine the conditions required to trigger convection in an ice I shell with a stress-, temperature-, and grain-size-dependent rheology measured in laboratory experiments by Goldsby and Kohlstedt [2001] (henceforth GK2001). Triggering convection from an initially conductive ice shell with a non-Newtonian rheology for ice I requires that a finite-amplitude temperature perturbation be issued to the ice shell [2]. Here, we characterize the amplitude and wavelength of temperature perturbation required to initiate convection in the outer ice I shells of Europa, Ganymede, and Callisto using the GK2001 rheology for a range of ice grain sizes.

Barr, Amy C.

Convective Instability in Ice I with Non-Newtonian Rheology: Application to the Galilean Satellites

At the temperatures and stresses associated with the onset of convection in an ice I shell of the Galilean satellites, ice behaves as a non-Newtonian fluid with a viscosity that depends on both temperature and strain rate. The convective stability of a non-Newtonian ice shell can be judged by comparing the Rayleigh number of the shell to a critical value. Previous studies suggest that the critical Rayleigh number for a non-Newtonian fluid depends on the initial conditions in the fluid layer, in addition to the thermal, rheological, and physical properties of the fluid. We seek to extend the existing definition of the critical Rayleigh number for a non-Newtonian, basally heated fluid by quantifying the conditions required to initiate convection in an ice I layer initially in conductive equilibrium. We find that the critical Rayleigh number for the onset of convection in ice I varies as a power (-0.6 to -0.5) of the amplitude of the initial temperature perturbation issued to the layer, when the amplitude of perturbation is less than the rheological temperature scale. For larger-amplitude perturbations, the critical Rayleigh number achieves a constant value. We characterize the critical Rayleigh number as a function of surface temperature of the satellite, melting temperature of ice, and rheological parameters so that our results may be extrapolated for use with other rheologies and for a generic large icy satellite. The values of critical Rayleigh number imply that triggering convection from a conductive equilibrium in a pure ice shell less than 100 km thick in Europa, Ganymede, or Callisto requires a large, localized temperature perturbation of a few kelvins to tens of kelvins to soften the ice and therefore may require tidal dissipation in the ice shell.

Barr, A. C.

Coarse-grained simulation of colloidal self-assembly, cation exchange, and rheology in Na/Ca smectite clay gels

Knowledge Gap: The aggregation of clay minerals—layered silicate nanoparticles—strongly impacts fluid flow, solute migration, and solid mechanics in soils, sediments, and sedimentary rocks. Experimental and computational characterization of clay aggregation is inhibited by the delicate water-mediated nature of clay colloidal interactions and by the range of spatial scales involved, from 1 nm thick platelets to flocs with dimensions up to micrometers or more. Simulations: Using a new coarse-grained molecular dynamics (CGMD) approach, we predicted the microstructure, dynamics, and rheology of hydrated smectite (more precisely, montmorillonite) clay gels containing up to 2,000 clay platelets on length scales up to 0.1 μm. Further, simulations investigated the impact of simulation time, platelet diameters (6 to 25nm), and the ratio of Na to Ca exchangeable cations on the assembly of tactoids (i.e., stacks of parallel clay platelets) and larger aggregates (i.e., assemblages of tactoids). We analyzed structural features including tactoid size and size distribution, basal spacing, counterion distribution in the electrical double layer, clay association modes, and the rheological properties of smectite gels. Findings: Our results demonstrate new potential to characterize and understand clay aggregation in dilute suspensions and gels on a scale of thousands of particles with explicit representation of counterion clouds and with accuracy approaching that of all-atom molecular dynamics (MD) simulations. For example, our simulations predict the strong impact of Na/Ca ratio on clay tactoid formation and the shear-thinning rheology of clay gels.

42 ENGINEERING

Mapping Structure and Rheology of pH-Responsive Resins for Low-VOC Coatings

In recent years, the paint and coatings industry has shifted away from traditional resin formulations that require high concentrations of volatile organic compounds (VOCs) to achieve the desired rheological performance and sustainability targets. One approach to eliminate or reduce VOCs in paint and coating formulations while maintaining the final performance is to disperse stimuli-responsive polymer latex particles in water. The chemistry and architecture of these particles have been engineered such that the suspension rheology changes in response to the pH changes. The particles can also be swollen with organic solvents to illicit similar rheological changes. To understand how the particle microstructure influences the observed macroscopic properties, we use small-angle neutron scattering and dynamic light scattering to determine that these particles consist of a cross-linked core with long polymer tails that extend into the dispersing medium. Carboxylic acid groups present on the tails deprotonate with increasing pH, and the extension of the polymer chain due to charge repulsion increases the hydrodynamic drag on the particle. Here we find that adjusting the pH alone has a much more significant effect on the shear dependence of the viscosity of the studied resin than adding organic solvent alone. We also find that this resin architecture is more responsive per mole of pH-responsive group than other architectures of pH-responsive latex particles in the literature.

36 MATERIALS SCIENCE

Effects of PLA/PHB Blend Ratio and Wood Flour Loading on the Melt Rheology and Thermomechanical Properties of Biobased Polymer Composites

The development of sustainable, biobased polymer composites is crucial for reducing supply chain dependence on fossil fuels. A major challenge lies in understanding and predicting the processability of these sustainable material alternatives, which directly impacts large-scale manufacturing. Here, this study systematically investigates the effect of poly(lactic acid) (PLA)/polyhydroxybutyrate (PHB) blend ratios and wood flour (WF) loadings on the thermal, rheological, and mechanical properties of the composites. Composites were prepared via melt compounding and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), oscillatory shear melt rheology, tensile testing, and scanning electron microscopy. Results showed that increasing the PHB content lowered the glass transition temperature, while higher PHB and WF loadings decreased thermal stability. Complex viscosity decreased with increasing PHB in 0 and 10% WF, whereas it increased in 20% and 30% WF for PHB-rich blends (80/20 and 70/30 PLA/PHB) due to stronger filler interactions with flexible PHB chains. At 30% WF, PHB-containing composites also showed elastic dominance with G′ higher than G″. This behavior was confirmed by van Gurp–Palmen plots, where the phase angle decreased with increasing PHB and WF loadings. WF addition also shifted Cole–Cole plots away from semicircular terminal relaxation, while time–temperature superposition validity was maintained, confirming that polymer chain dynamics continue to dominate melt behavior. Young’s modulus increased with WF loading, while tensile strength and toughness decreased due to weaker interfacial adhesion between the matrix and the filler. Interestingly, 10% WF systems containing PHB exhibited the highest toughness among all of the filled systems, indicating synergistic reinforcement from WF fillers and PHB-induced ductility. Overall, melt rheology effectively captured the internal structure and stiffness of the composites as the formulation changed, reinforcing the concept that the PLA/PHB ratio and WF content can be tuned to adjust melt elasticity and balance mechanical property trade-offs for targeted applications.

melt rheology

Large-Scale Compatibilization of Postconsumer Polyolefins in the Presence of Paraffin Wax as a Rheology Modifier

Postconsumer polyolefins (r-POs) are leading plastic waste contributors today. This study reports, for the first time, the compatibilization of r-POs at a 50 kilogram (kg) scale with a styrene block copolymer compatibilizer in the presence of paraffin waxes as rheology modifiers (RMs). The addition of the rheological modifier (RM) and compatibilizer enhances the melt flow indices (MFIs) and mechanical properties, respectively. One aspect of this study is to compare the effectiveness of low-cost paraffin wax to that of specialized and expensive RMs in r-POs. The mechanical and rheological properties such as the melt flow index (MFI) of r-POs were compared in the presence of two types of RMs. Next, the study explores the challenges encountered when scaling the compatibilization of r-POs in the presence of paraffin wax from a 10-g to a 50-kg scale. The mechanical properties were determined and compared for samples at different scales. The study further investigated the effect of the method used for blending paraffin wax with r-PO and its impact on the value of their MFI and mechanical properties. This at-scale validation could pave the way for the commercialization of r-POs.

crystallinity