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At least 109 records · Page 6

Rheology and stability of nanoparticle-stabilized CO 2 foam under reservoir conditions

This work investigates the rheology and stability of nanoparticle-stabilized CO 2 foams under reservoir conditions (high temperature and high pressure) for fracturing applications. The effects of different parameters on foam apparent viscosity and foam stability were experimentally investigated including the effects of nanoparticle concentration, salinity, foam quality (Γ), shear rate and temperature. The power law model was applied to calculate foam apparent viscosity owing to its pseudo-plastic behavior, and the changes of foam heights over time were used to evaluate foam stability. Results showed that the CO 2 foam apparent viscosity featured a mountain-shaped curve versus Γ, with the peak apparent viscosity obtained at 70% foam quality. The increase of salinity (up to 11%) in the continuous phase improved both foam stability and rheology. Higher nanoparticle concentration could contribute to better foam stability, but there was a threshold concentration, above which the foam apparent viscosity remained stabilized. The CO 2 foam stabilized by nanoparticles displayed a shear-thickening behavior as the experiment flow rate increased from 6 mL/min to 18 mL/min. Further studies showed that as the total flow rate increased, the CO 2 foam became finer-textured with better stability. Elevated temperatures could undermine foam apparent viscosity and long-term stability. The results of this study could provide guidelines as to the design of foam fracturing systems for field applications.

03 NATURAL GAS↗

Effects of 2D filler on rheology of additive manufacturing polymers: Simulation and experiment on polyetherketoneketone-mica composites

Polymeric composites have attracted increasing interest in fundamental studies and industrial applications due to their often-superior characteristics over conventional pure polymers. In this work, we studied the relationship between the rheological properties, critical in processing methods such as additive manufacturing, and the structure of a polymer-2D filler system by experiment and simulation methods. Considering the high performance polymer polyetherketoneketone (PEKK) with 2D filler (mica) composite as an example, the effects of filler size, filler content, surface chemistry and shear rate were systematically investigated. Here, it is demonstrated that the interaction between the polymer and 2D filler brings two different consequences on tuning the viscosity of polymer-filler composite. The stronger interaction increases the shear stress of the polymer-2D filler composite system, leading to higher viscosity. On the other hand, the stronger interaction can promote more absorption of polymer chains on the surface, which makes the local polymer network disentangled and decreases the continuous viscosity from the polymer network. This work provides a fundamental understanding on the relationship between macroscopic rheological properties and the structural properties and energetics at molecular level of polymer-2D filler composite.

36 MATERIALS SCIENCE↗

Sodium dodecyl sulfate modulates the structure and rheological properties of Pluronic F108–poly(acrylic acid) coacervates)

Micelles formed within coacervate phases can impart functional properties, but it is unclear if this micellization provides mechanical reinforcement of the coacervate whereby the micelles act as high functionality crosslinkers. Here, we examine how sodium dodecyl sulfate (SDS) influences the structure and properties of Pluronic F108–polyacrylic acid (PAA) coacervates as SDS is known to decrease the aggregation number of Pluronic micelles. Increasing the SDS concentration leads to larger water content in the coacervate and an increase in the relative concentration of PAA to the other solids. Rheological characterization with small angle oscillatory shear (SAOS) demonstrates that these coacervates are viscoelastic liquids with the moduli decreasing with the addition of the SDS. The loss factor (tan δ) initially increases linearly with the addition of SDS, but a step function increase in the loss factor occurs near the reported CMC of SDS. However, this change in rheological properties does not appear to be correlated with any large scale structural differences in the coacervate as determined by small angle X-ray scattering (SAXS) with no signature of Pluronic micelles in the coacervate when SDS concentration is >4 mM during formation of the coacervate, which is less than that observed (6 mM SDS) in initial Pluronic F108 solution despite the higher polymer concentration in the coacervate. Finally, these results suggest that the mechanical properties of polyelectrolyte-non-ionic surfactant coacervates are driven by the efficicacy of binding between the complexing species driving the coacervate, which can be disrupted by competitive binding of the SDS to the Pluronic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relaxation dynamics of deformed polymer nanocomposites as revealed by small-angle scattering and rheology

Here, the relaxation dynamics of polystyrene (PS)/silica nanocomposites after a large step deformation are studied by a combination of small-angle scattering techniques and rheology. Small-angle X-ray scattering measurements and rheology show clear signatures of nanoparticle aggregation that enhances the mechanical properties of the polymer nanocomposites (PNCs) in the linear viscoelastic regime and during the initial phase of stress relaxation along with accelerated relaxation dynamics. Small-angle neutron scattering experiments under the zero-average-contrast condition reveal, however, smaller structural anisotropy in the PNCs than that in the neat polymer matrix, as well as accelerated anisotropy relaxation. In addition, the degrees of anisotropy reduction and relaxation dynamics acceleration increase with increasing nanoparticle loading. These results are in sharp contrast to the prevailing viewpoint of enhanced molecular deformation as the main mechanism for the mechanical enhancement in PNCs. Furthermore, the observed acceleration of stress relaxation and reduction in structural anisotropy point to two types of nonlinear effects in the relaxation dynamics of PNCs at large deformation.

36 MATERIALS SCIENCE↗

Rheological dynamics and structural characteristics of supramolecular assemblies of β-cyclodextrin and sulfonic surfactants

Cyclodextrins are highly functional compounds with a hydrophobic cavity capable of forming supramolecular inclusion complexes with various classes of molecules including surfactants. The resultant rich nanostructures and their dynamics are an interesting research problem in the area of soft condensed matter and related applications. In this paper, we report novel dynamical supramolecular assemblies based on the complexation of β-cyclodextrin with 3 different sulfonic surfactants, which are sodium hexadecylsulfate, sodium dodecylbenzenesulfonate, and myristyl sulfobetaine. It was observed that a β-cyclodextrin : surfactant/2 : 1 molar ratio was ideal for inducing axial growth and imparting large viscosities in the suspensions. Such complexation processes were accompanied by intriguing nanostructural phase behaviors and rheological properties that were very sensitive to the molecular architecture of sulfonic surfactants. The presence of an amino group in the head group of the surfactant allowed for large viscosities that reached 2.4 × 10 4 Pa s which exhibited gel-like behavior. In contrast, smaller viscosity values with a lower consistency index were observed when a bulky aromatic ring was present instead. DIC microscopy was used to visually probe the microstructure of the systems with respect to sulfonate molecular architecture. Additionally, surface tension measurements, and FTIR and NMR spectroscopies were used to gain insights into the nature of interactions that lead to the complexation and nanostructural characteristics. Finally, mechanics correlating the supramolecular morphologies to the rheological properties were proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous inference of plate boundary stresses and mantle rheology using adjoints: large-scale 2-D models

SUMMARY Plate motions are a primary surface constraint on plate and mantle dynamics and rheology, plate boundary stresses and the occurrence of great earthquakes. Within an optimization method, we use plate motion data to better constrain uncertain mantle parameters. For the optimization problem characterizing the maximum a posteriori rheological parameters we derive gradients using adjoints and expressions to approximate the posterior distributions for stresses within plate boundaries. We apply these methods to a 2-D cross section from the western to eastern Pacific, with temperature distributions and fault zone geometries developed primarily from seismic and plate motion data. We find that the best-fitting stress exponent, n, is about 2.8 and the yield stress about 100 MPa or less. The normal stress on the interplate fault zones is about 100 MPa and the shear stresses about 10 MPa or less.

Rudi, Johann (ORCID:0000000265639265)↗

Rheology of dense fiber suspensions: Origin of yield stress, shear thinning, and normal stress differences

We explain the origins of yield stress, shear thinning, and normal stress differences in rigid fiber suspensions. We investigate the interplay between the hydrodynamic, noncontact attractive and repulsive, and interfiber contact interactions. The shear-thinning viscosity and finite yield stress obtained from the Immerse Boundary Method simulations are in quantitative agreement with experiential results from the literature. In this study, we show that attractive interactions result in yield stress and shear thinning rheology in the suspensions of rigid fibers. This is an important finding, given the ongoing discussion regarding the origin of the yield stress for suspensions of fibers. Finally, the ability of the proposed model to quantitatively predict the rheology is not limited to only shear thinning and yield stress but also extends to normal stresses.

42 ENGINEERING↗

Composite entanglement topology and extensional rheology of symmetric ring-linear polymer blends

Extensive molecular simulations are applied to characterize the equilibrium dynamics, entanglement topology, and nonlinear extensional rheology of symmetric ring-linear polymer blends with systematically varied ring fraction ϕR. Chains with degree of entanglement Z≈14 are mixed to produce 10 well-entangled systems with ϕR varying from neat linear to neat ring melts. Z is large enough that except for very large ϕR, the rings are threaded by multiple linear chains in equilibrium. Primitive path analysis is used to visualize and quantify the structure of the composite ring-linear entanglement network. We measure the quantity of ring-linear threading and linear-linear entanglement as a function of ϕR and identify with simple arguments a ring fraction ϕR≈0.4 where the topological constraints of the composite entanglement network are maximized. These topological analyses are used to rationalize the ϕR-dependence of ring and linear chain dynamics, conformations, and rheology. Simulations of startup uniaxial elongation flows demonstrate the extensional stress overshoot observed in recent filament stretching experiments and characterize how it depends on the blend composition and entanglement topology. The overshoot is driven by an overstretching and recoil of ring polymers due to the convective unthreading of rings from linear chains.

O’Connor, Thomas C.↗

Strain shift measured from stress-controlled oscillatory shear: Evidence for a continuous yielding transition and new techniques to determine recovery rheology measures

Understanding the yielding of complex fluids is an important rheological challenge that affects our ability to engineer and process materials for a wide variety of applications. Common theoretical understandings of yield stress fluids follow the Oldroyd–Prager formalism in which the material behavior below the yield stress is treated as solidlike, and above the yield stress as liquidlike, with an instantaneous transition between the two states. This formalism was built on a quasi-static approach to the yield stress, while most applications, ranging from material processing to end user applications, involve a transient approach to yielding over a finite timescale. Using stress-controlled oscillatory shear experiments, we show that yield stress fluids flow below their yield stresses. This is quantified through measuring the strain shift, which is the value about which the strain oscillates during a stress-controlled test and is a function of only the unrecoverable strain. Measurements of the strain shift are, therefore, measurements of flow having taken place. These experimental results are compared to the Herschel–Bulkley form of the Saramito model, which utilizes the Oldroyd–Prager formalism, and the recently published Kamani–Donley–Rogers (KDR) model, in which one constitutive equation represents the entire range of material responses. Scaling relationships are derived, which allow us to show why yield stress fluids will flow across all stresses, above and below their yield stress. Finally, derivations are presented that show strain shift can be used to determine average metrics previously attainable only through recovery rheology, and these are experimentally verified.

Mechanics↗

Rheological Properties of Small-Molecular Liquids at High Shear Strain Rates

Molecular-scale understanding of rheological properties of small-molecular liquids and polymers is critical to optimizing their performance in practical applications such as lubrication and hydraulic fracking. We combine nonequilibrium molecular dynamics simulations with two unsupervised machine learning methods: principal component analysis (PCA) and t-distributed stochastic neighbor embedding (t-SNE), to extract the correlation between the rheological properties and molecular structure of squalane sheared at high strain rates (10 6 –10 10 s -1 ) for which substantial shear thinning is observed under pressures P ϵ 0.1–955 MPa at 293 K. Intramolecular atom pair orientation tensors of 435 × 6 dimensions and the intermolecular atom pair orientation tensors of 61 × 6 dimensions are reduced and visualized using PCA and t-SNE to assess the changes in the orientation order during the shear thinning of squalane. Dimension reduction of intramolecular orientation tensors at low pressures P = 0.1,100 MPa reveals a strong correlation between changes in strain rate and the orientation of the side-backbone atom pairs, end-backbone atom pairs, short backbone-backbone atom pairs, and long backbone-backbone atom pairs associated with a squalane molecule. At high pressures P ≥ 400 MPa, the orientation tensors are better classified by these different pair types rather than strain rate, signaling an overall limited evolution of intramolecular orientation with changes in strain rate. Dimension reduction also finds no clear evidence of the link between shear thinning at high pressures and changes in the intermolecular orientation. The alignment of squalane molecules is found to be saturated over the entire range of rates during which squalane exhibits substantial shear thinning at high pressures.

36 MATERIALS SCIENCE↗

New generalized rheological model for lubrication of a ball spinning in a nonconforming groove

The elastohydrodynamic theory for predicting the spinning friction of a ball in a nonconforming groove was modified to incorporate a rheological model. The rheological model is based on the exponential pressure viscosity relation for low shear stresses, but at high shear rates and pressures, the relation is altered to one in which the shear stress is porportional to the normal stress. The model was fitted to experimental spinning torques for four different lubricants: a synthetic paraffinic lubricant, di-2-ethylhexyl sebacate, a super-refined naphthenic mineral oil, and a polyphenyl ether (5P4E). Good agreement between the model and experiment was found.

Allen, C. W.↗

Investigations of lubricant rheology as applied to elastohydrodynamic lubrication

Measurements of lubricant shear rheological behavior in the amorphous solid region and near the liquid-solid transition are reported. Elastic, plastic and viscous behavior was observed. A shear rheological model based on primary laboratory data is proposed for concentrated contact lubrication. The model is a Maxwell model modified with a limiting shear stress. Three material properties are required: low shear stress viscosity, limiting elastic shear modulus, and the limiting shear stress the material can withstand. All three are functions of temperature and pressure. In applying the model to EHD contacts the predicted response possesses the characteristics expected from several experiments reported in the literature.

Bair, S.↗

Rheology of composite solid propellants during motor casting

Results of casting studies are reviewed so as to define the viscosity criteria insuring the fabrication of defect-free grains. The rheology of uncured propellants is analyzed showing that a realistic assessment of a propellant's flow properties must include measurement of viscosity as a function of shear stress and time after curing agent. Methods for measuring propellant viscosity are discussed, with particular attention given to the Haake-Rotovisko rotational viscometer. The effects of propellant compositional and processing variables on apparent viscosity are examined, as are results relating rheological behavior to grain defect formation during casting.

Klager, K.↗

Seismic velocity, attenuation and rheology of the upper mantle

Seismic and rheological properties of the upper mantle in the vicinity of the low-velocity zone are expressed in terms of relaxation by dislocation glide. Dislocation bowing in the glide plane explains seismic velocities and attenuation. Climbing at higher stresses for longer periods of time give the observed viscosity, and explain the low velocity and high temperature attenuation found at seismic frequencies. Due to differing parameters, separate terms for thermal, seismic and rheological lithospheres are proposed. All three lithospheres, however, are related and are functions of temperature, and must be specified by parameters such as period, stress, and stress duration.

Anderson, D. L.↗

Chemical and rheological evaluation of polymides

Chemical and rheological evaluation techniques were developed for polyimide composite matrix resins. LARC 160 (AP-22), LARC 160 (Curithane 103), PMR 15 and PISO2 resins were investigated. Liquid and solid state rheological techniques were used to develop processing parameters and woven graphite reinforced laminates were successfully fabricated, using these processing parameters.

Maximovich, M.↗

Rheologies of H2O ices Ih, II, and III at high pressures - A progress report

Ordinary hexagonal ice (ice Ih) represents the stable crystalline form of H2O on the earth's surface. It is known that ice exists elsewhere in the solar system. Thus, several of the moons of Saturn and Jupiter are composed predominately of H2O and their surface temperatures are about 75 and 100 K. The pressures in the interior of some of the larger of the moons may be as high as 3 GPa. The involved pressures and temperatures extend far beyond the conditions over which the rheological laws for ice Ih can be confidently extrapolated. It is, therefore, necessary to obtain information regarding the rheologies of H2O ices in pressure and temperature ranges which had not yet been previously considered. Since 1981, over 100 triaxial compression tests have been conducted over a wide range of temperatures (77 to 258 K) and pressures (0.1 to 350 MPa). The present paper provides a progress report of these experiments.

Kirby, S. H.↗

On transient rheology and glacial isostasy

The effect of transient creep on the inference of long-term mantle viscosity is investigated using theoretical predictions from self-gravitating, layered earth models with Maxwell, Burgers' body, and standard linear solid rheologies. The interaction between transient and steady-state rheologies is studied. The responses of the standard linear solid and Burgers' body models to transient creep in the entire mantle, and of the Burgers' body and Maxwell models to creep in the lower mantle are described. The models' responses are examined in terms of the surface displacement, free air gravity anomaly, wander of the rotation pole, and the secular variation of the degree 2 zonal coefficient of the earth's gravitational potential field. The data reveal that transient creep cannot operate throughout the entire mantle.

Yuen, David A.↗

Effects from equation of state and rheology in dissipative heating in compressible mantle convection

The effects of compressibility on mantle convection are considered, incorporating the effects of equations of state and rheology in the dissipative heating term of the energy equation. The ways in which compression may raise the interior mantle temperature are explicitly demonstrated, and it is shown how this effect can be used to constrain some of the intrinsic parameters associated with the equation of state in the mantle. It is concluded that the coupling between variable viscosity and equation of state in dissipative heating is potentially an important mechanism in mantle convection. These findings emphasize that rheology, equation of state, and radiogenic heating are all linked to each other by nonlinear thermomechanical couplings.

Yuen, David A.↗