Macrorheological Measurements Research Articles

Nanoscopic Interfacial Hydrogel Viscoelasticity Revealed from Comparison of Macroscopic and Microscopic Rheology.

Deviations between macrorheological and particle-based microrheological measurements are often considered to be a nuisance and neglected. We study aqueous poly(ethylene oxide) (PEO) hydrogels for varying PEO concentrations and chain lengths that contain microscopic tracer particles and show that these deviations reveal the nanoscopic viscoelastic properties of the particle-hydrogel interface. Based on the transient Stokes equation, we first demonstrate that the deviations are not due to finite particle radius, compressibility, or surface-slip effects. Small-angle neutron scattering rules out hydrogel heterogeneities. Instead, we show that a generalized Stokes-Einstein relation, accounting for an interfacial shell around tracers with viscoelastic properties that deviate from bulk, consistently explains our macrorheological and microrheological measurements. The extracted shell diameter is comparable to the PEO end-to-end distance, indicating the importance of dangling chain ends. Our methodology reveals the nanoscopic interfacial rheology of hydrogels and is applicable to different kinds of viscoelastic fluids and particles.

An optimized protocol for assessment of sputum macrorheology in health and muco-obstructive lung disease

Background: Airway mucus provides important protective functions in health and abnormal viscoelasticity is a hallmark of muco-obstructive lung diseases such as cystic fibrosis (CF). However, previous studies of sputum macrorheology from healthy individuals and patients with CF using different experimental protocols yielded in part discrepant results and data on a systematic assessment across measurement settings and conditions remain limited. Objectives: The aim of this study was to develop an optimized and reliable protocol for standardized macrorheological measurements of airway mucus model systems and native human sputum from healthy individuals and patients with muco-obstructive lung disease. Methods: Oscillatory rheological shear measurements were performed using bovine submaxillary mucin (BSM) at different concentrations (2% and 10% solids) and sputum samples from healthy controls (n = 10) and patients with CF (n = 10). Viscoelastic properties were determined by amplitude and frequency sweeps at 25°C and 37°C with or without solvent trap using a cone-plate geometry. Results: Under saturated atmosphere, we did not observe any temperature-dependent differences in 2% and 10% BSM macrorheology, whereas in the absence of evaporation control 10% BSM demonstrated a significantly higher viscoelasticity at 37°C. Similarly, during the measurements without evaporation control at 37°C we observed a substantial increase in the storage modulus G′ and the loss modulus G″ of the highly viscoelastic CF sputum but not in the healthy sputum. Conclusion: Our data show systematically higher viscoelasticity of CF compared to healthy sputum at 25°C and 37°C. For measurements at the higher temperature using a solvent trap to prevent evaporation is essential for macrorheological analysis of mucus model systems and native human sputum. Another interesting finding is that the viscoelastic properties are not much sensitive to the applied experimental deformation and yield robust results despite their delicate consistency. The optimized protocol resulting from this work will facilitate standardized quantitative assessment of abnormalities in viscoelastic properties of airway mucus and response to muco-active therapies in patients with CF and other muco-obstructive lung diseases.

Assessment of Interaction Behaviors of Cement-Emulsified Asphalt Based on Micro-Morphological and Macro-Rheological Approaches.

Cement emulsified asphalt composite binder (CEACB) plays a determining role in the construction of cold recycled asphalt pavements. Understanding the interaction behaviors of cement-emulsified asphalt is very essential to promote the serviceability of CEACB. The objective of this study was to explore the interaction behaviors and mechanism of cement-emulsified asphalt associated with microstructural characteristics and to assess the interaction ability of cement-emulsified asphalt by performing macro-rheological measurements. Firstly, the physico-chemical interaction of cement-emulsified asphalt was qualitatively discussed by analyzing the difference of characteristic peaks based on Fourier transform infrared (FTIR) spectrometer. Secondly, the micro-morphological evolution behaviors of CEACB attributing to the cement-emulsified asphalt interaction were investigated by using a fluorescence microscope (FM) and laser particle size analyzer (LPSA). Thirdly, the microstructural characteristics of CEACB were studied by observing the spatial network structure through the scanning electron microscopy (SEM). Finally, the macro-rheological index based on dynamic rheological shear (DSR) test was proposed to evaluate the interaction ability of cement-emulsified asphalt. The results show that the cement-emulsified asphalt interaction is merely a physical blending process due to the occurrence of no new characteristic peaks in the FTIR spectrum except for cement hydration products. The cement-emulsified asphalt interaction in early-age CEACB could be reflected by the aggregation process among asphalt droplets and the adsorption action of cement particles to asphalt droplets. A reasonable ratio of cement to emulsified asphalt could promote the formation of the denser spatial network structure of CEACB along with cement hydration products growing and interweaving with asphalt films. The K-B- index based on macro-rheological properties of CEACB with full consideration of cement hydration process is very suitable for evaluating the interaction ability of cement-emulsified asphalt under the condition of different cement proportions and curing time. The research would provide the support for understanding the natural properties of CEACB and promote the improvement of the mechanical performance of cold recycled asphalt pavements.

Slippery flows of a Carbopol gel in a microchannel

The ability to predict and/or control wall slip is a fundamental problem in the hydrodynamics of yield stress fluids, which is poorly understood to date and has important applications in bio- and micro-fluidic systems. Systematic measurements of steady flows of a simple yield stress fluid (Carbopol Ultrez 10) in a plane acrylic micro-channel are used to establish rigorous scaling laws for the wall velocity gradient and the slip velocity. By means of epi-fluorescent microscopy combined with a custom developed Digital Particle Image Velocimetry (DPIV) technique, times series of velocity fields were measured within a wide range of flow rates and three distinct flow regimes were identified: full plug, partial plug and fully yielded. Corresponding to each flow regime, wall velocity gradients and slip velocities were obtained by extrapolating the velocity profiles using a smoothing spline function. By combining the flow field measurements with the macro-rheological measurements, scaling laws for the wall velocity gradient and the slip velocity with the wall shear stress were identified, and compared with results from the literature. Detailed microscopic measurements of the velocity field enabled an assessment of the effectiveness of a chemical treatment of the channel walls meant to suppress wall slip proposed by Metivier and coworkers in Ref. [1].

Characteristics and Mechanisms of Asphalt-Filler Interactions from a Multi-Scale Perspective.

Asphalt mastic plays an important role in asphalt mixtures for pavement engineering. Understanding the asphalt–filler interaction behavior is essential to improve the pavement performance of asphalt mastics. The objective of this paper was to evaluate the asphalt–filler interaction ability based on macro-rheological measurements and to investigate the asphalt–filler interaction mechanism associated with microstructural characteristics of asphalt mastics. First, the asphalt–filler interaction was characterized using macro-rheological features of asphalt mastics based on dynamic shear rheometer (DSR) tests. Second, the physico-chemical interaction between the asphalt and filler was qualitatively evaluated using a Fourier transform infrared (FTIR) spectrometer. Third, the asphalt–filler interaction behavior was investigated in terms of the micro-morphological properties of mineral fillers and asphalt mastics by conducting scanning electron microscopy (SEM) and atomic force microscope (AFM) tests. Finally, the grey relational analysis (GRA) was employed to identify the correlation between the properties of mineral fillers and the macro–micro performances of asphalt mastics. The results show that a higher content of alkaline mineral filler within the critical volume fraction range produced a greater interaction ability between the asphalt and filler. The asphalt–filler interaction is mainly a physical action since no obvious new adsorption peaks appeared in the FTIR spectrum. The micro-morphological characteristics of asphalt mastic mainly depended on the adsorption effect of mineral fillers on polar fractions and the dispersion effect of mineral fillers on wax crystals in the asphalt binder. Based on the results of the GRA, the acidity and content of mineral fillers exhibited a great influence on the micro-morphological and macro-rheological characteristics of asphalt mastics, and the specific surface area of the mineral filler exerted a significant influence on the asphalt–filler interaction ability. Furthermore, the K-B- index was more appropriate for evaluating the asphalt–filler interaction ability.

Investigations to Evaluate Gastric Mucoadhesion of an Organic Product to Ameliorate Gastritis.

Gastritis is an inflammatory disease leading to abdominal pain, nausea, and diarrhea. While therapy depends on etiology, adhesive agents protecting the gastric tissue represent a promising treatment option. Caricol®-Gastro is an organic product that significantly decreased gastritic abdominal pain in a recent clinical study. To investigate whether this beneficial effect can be attributed to the formation of a protective layer covering the gastric mucosa after oral application, several methods were used to determine adhesion. These include macro-rheological measurements and gastric mucin interactions, which were correlated to network formation, examined by Cryo-scanning electron microscopy technique, wettability via sessile drop method on human gastric adenocarcinoma cell layers, and ex vivo adhesion studies on gastric porcine tissue with the falling liquid film technique considering physiological conditions and Franz diffusion cells for quantification. The results showed that Caricol®-Gastro formed a stable viscoelastic network with shear thinning properties. It exhibited high wettability and spreadability and adhered to the excised gastric mucosa. We found that oat flour, as the main ingredient of Caricol®-Gastro, supports the gel network regarding viscoelasticity and, to a lesser extent, adhesion in a concentration dependent manner. Moreover, our data highlight that a variety of coordinated methods are required to investigate gastric adhesion.

A phenomenological approach of solidification of polymeric phase change materials

Phase Change Materials (PCMs) are widely used in thermal energy storage and thermal management systems due to their small volume for a given stored energy and their capability for maintaining nearly constant temperatures. However, their performance is limited by their low thermal conductivity and possible leaks while in the liquid phase. One solution is to imprison the PCM inside a polymer mesh to create a Polymeric Phase Change Material (PPCM). In this work, we have studied the cooling and solidification of five PPCMs with different PCMs and polymer fractions. To understand the heat transfer mechanisms involved, we have carried out micro- and macrorheological measurements in which Brownian motion of tracers embedded in PPCMs has been depicted and viscoelastic moduli have been measured, respectively. Beyond a given polymer concentration, it was shown that the Brownian motion of the tracers is limited by the polymeric chains and that the material exhibits an elastic behavior. This would suggest that heat transfer essentially occurs by conduction, instead of convection. Experiments were conducted to measure temperature variation during cooling of the five samples, and a semi-empirical model based on a phenomenological approach was proposed as a practical tool to choose and size PPCMs.

Dynamics of magnetic nanoparticles in viscoelastic media

We compare different models for the description of the complex susceptibility of magnetic nanoparticles in an aqueous gelatin solution representing a model system for a Voigt-Kelvin scheme. The analysis of susceptibility spectra with the numerical model by Raikher et al. [7] is compared with the analysis applying a phenomenological, modified Debye model. The fit of the models to the measured data allows one to extract the viscoelastic parameter dynamic viscosity η and shear modulus G. The experimental data were recorded on single-core thermally blocked CoFe2O4 nanoparticles in an aqueous solution with 2.5wt% gelatin. Whereas the dynamic viscosities obtained by fitting the model – extended by distributions of hydrodynamic diameters and viscosities – agree very well, the derived values for the shear modulus show the same temporal behavior during the gelation process, but vary approximately by a factor of two. To verify the values for viscosity and shear modulus obtained from nanorheology, macrorheological measurements are in progress.

Magnetic microrods as a tool for microrheology.

Dynamics of superparamagnetic rods in crossed constant and alternating magnetic fields as a function of field frequency are studied and it is shown that above the critical value of the amplitude of the alternating field the rod oscillates around the direction of the alternating field. The fit of the experimentally measured time dependence of the mean orientation angle of the rod allows one to determine the ratio of magnetic and viscous torques which act on the rod. The protocol of microrheological measurements consists of recording the dynamics of the orientation of the rod when the magnetic field is applied at an angle to the rod and observing its relaxation due to the accumulated elastic energy after the field is switched off. The microrheological data obtained are in reasonable agreement with the macrorheological measurements.

Field-dependent anisotropic microrheological and microstructural properties of dilute ferrofluids.

We have measured microrheological and microstructural properties of a superparamagnetic ferrofluid made of Mn0.75Zn0.25Fe2O4 (MZF) nanoparticles, using passive microrheology in a home-built inverted microscope. Thermal motion of a probe microsphere was measured for different values of an applied external magnetic field and analysed. The analysis shows anisotropy in magneto-viscous effect. Additional microrheological properties, such as storage modulus and loss modulus and their transition are also seen. We have also obtained microstructural properties such as elongational flow coefficient [Formula: see text] , relaxation time constant [Formula: see text] , coefficient of dissipative magnetization [Formula: see text] , etc., using the analysis given in Oliver Muller et al., J. Phys.: Condens. Matter 18, S2623, (2006) and Stefan Mahle et al., Phys. Rev. E 77, 016305 (2008) over our measured viscosity data. Our values for the above parameters are in agreement with earlier theoretical calculations and macro-rheological experimental measurements. These theoretical calculations consider an ideal situation of zero-shear limit, which is best approximated only in the passive microrheology technique described here and a first time measurement of all these parameters with passive microrheology.

Micro and macrorheology at fluid-fluid interfaces.

Interfacial transport phenomena play an important role in the dynamics of liquid interfaces found in emulsions, foams, and membranes. Both macroscopic and microscopic measurements of interfacial transport and rheology can be made, the former typically relying on the use of at least millimeter-scale probes, and the latter exploiting the motion of micrometer-scale probes. Recent publications have shown multiple orders of magnitude differences between experimentally observed diffusivities in passive microrheology, and the diffusivities expected based on macroscopic measurements of the surface rheology. In the present work, interfacial rheological measurements were made with both microrheological and macrorheological methods and the results are compared for different monolayers at an air-water interface. We have identified multiple aspects of particle-tracking microrheology that can contribute to orders-of-magnitude disagreement with macrorheological methods. In particular, unintentional tracking of particles not residing at the interface, the presence of large-scale interfacial heterogeneities, and underestimating static noise can all decrease estimates of surface viscosity from particle-tracking microrheology by orders of magnitude. After taking care to address these artifacts, we show that viscosities obtained from both methods agree well for poly(tert-butyl methacrylate) (PtBMA), and for dipalmitoylphosphatidylcholine (DPPC), but disagree by orders of magnitude for hexadecanol. In poly(tert-butyl acrylate) (PtBA), large-scale heterogeneities prevented us from obtaining representative surface viscosities. By making surface viscosity measurements in an interfacial stress rheometer (ISR) with needles of different aspect ratio, we show that compressibility or Marangoni stress related effects may be contributing to the orders of magnitude disagreement in micro and macrorheological measurements observed in the hexadecanol system.

Calibration of an optical tweezer microrheometer by sequential impulse response

We report a robust method for calibrating optical tweezers in any viscoelastic medium. This approach uses two coupled measurements—one from a static experiment in which a trapped particle diffuses passively within the tweezer's harmonic potential and another from a dynamic experiment in which the trap is jumped discontinuously to a new position while the particle undergoes transient relaxation back into the minimum of the optical potential. Together, these are sufficient to determine the stiffness of the trap in a material of unknown rheology. The method is tested in a Newtonian fluid and compares favorably with other means of calibration. The calibration is also per- formed in a non-Newtonian fluid of which standard optical tweezer calibration methods may struggle to characterize. The correctly calibrated optical tweezer microrheometer measures the rheology of polymer solutions in agreement with macrorheological measurements.

Micro- and Macrorheology of Jellyfish Extracellular Matrix

Mechanical properties of the extracellular matrix (ECM) play a key role in tissue organization and morphogenesis. Rheological properties of jellyfish ECM (mesoglea) were measured in vivo at the cellular scale by passive microrheology techniques: microbeads were injected in jellyfish ECM and their Brownian motion was recorded to determine the mechanical properties of the surrounding medium. Microrheology results were compared with macrorheological measurements performed with a shear rheometer on slices of jellyfish mesoglea. We found that the ECM behaved as a viscoelastic gel at the macroscopic scale and as a much softer and heterogeneous viscoelastic structure at the microscopic scale. The fibrous architecture of the mesoglea, as observed by differential interference contrast and scanning electron microscopy, was in accord with these scale-dependent mechanical properties. Furthermore, the evolution of the mechanical properties of the ECM during aging was investigated by measuring microrheological properties at different jellyfish sizes. We measured that the ECM in adult jellyfish was locally stiffer than in juvenile ones. We argue that this stiffening is a consequence of local aggregations of fibers occurring gradually during aging of the jellyfish mesoglea and is enhanced by repetitive muscular contractions of the jellyfish.

Passive and Active Microrheology of Hard-sphere Colloids

We performed passive and active microrheology using probe particles in a bath of well-characterized, model hard-sphere colloids in the fluid state over the whole range of volume fractions below the glass transition. The probe and bath particles have nearly the same size. Passive tracking of probe particles yields short-time self-diffusion coefficients. Comparison with literature data demonstrates that the interaction between probe and bath particles is hard-sphere-like. The short-time diffusivities yield one set of microviscosities as a function of volume fraction, which agrees with previous macrorheological measurements of the high-frequency viscosity of hard-sphere colloids. Using optical tweezers, we measure the force on a trapped probe particle as the rest of the sample is translated at constant velocity. This yields a second set of microviscosities at high Péclet numbers. These agree with previous macrorheological measurements of the high-shear viscosity of similar colloids, at shear-rates below the onset of shear-thickening.

Cross-Linking Molecules Modify Composite Actin Networks Independently

While cells make use of many actin binding proteins (ABPs) simultaneously to tailor the mechanical properties of the cytoskeleton, the detailed interplay of different ABPs is not understood. By a combination of macrorheological measurements and confocal microscopy, we show that the ABPs fascin and filamin modify the structural and viscoelastic properties of composite in vitro actin networks independently. The outnumbering ABP dictates the local network structure and therefore also dominates the macromechanical network response.

Morphological determinants of red cell deformability.

The influence of cellular morphology on the rheological behaviour of human red blood cells (RBC) and RBC suspensions has been examined for both fresh and ATP-depleted erythrocytes. Macrorheological measurements were made using a cone-plate viscometer and microrheological measurements included cell deformation by high-speed centrifugation and direct microscopic observation using a counter-rotating rheoscope. Evaluation of the experimental observations indicates the importance of RBC shape as a determinant of RBC deformability, such that either echinocytic or stomatocytic shape alterations result in increased deformability. Thus, cellular morphology, in addition to S/V ratio, membrane and cytoplasmic material properties must be considered in assessing the response of the cell to deforming forces. It is to be noted, however, that these morphology effects are shear-stress dependent and may escape detection in systems in which high stress levels are employed, e.g. micropore filtration using large pressure gradients.