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Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

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Dissolving small amounts of polymer into a Newtonian fluid can dramatically change the dynamics of transitional and turbulent flows. We investigate the spatiotemporal dynamics of a submerged jet of dilute polymer solution entering a quiescent bath of Newtonian fluid. High-speed digital Schlieren imaging is used to quantify the evolution of Lagrangian features in the jet revealing a rich sequence of transitional and turbulent states. At high levels of viscoelasticity, we identify a new distinct transitional pathway to elastoinertial turbulence (EIT) that does not feature the conventional turbulent bursts and instead proceeds via a shear-layer instability that produces elongated filaments of polymer due to the nonlinear effects of viscoelasticity. Even though the pathways to the EIT state can be different, and within EIT the spatial details of the turbulent structures vary systematically with polymer microstructure and concentration, there is a universality in the power-law spectral decay of EIT with frequency, f^{-3}, independent of fluid rheology and flow parameters.

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Characterizing and understanding the viscoelastic mechanical properties of natural and synthetic fibers is of great importance in many biological and industrial applications. Microscopic techniques such as micro/nano indentation have been successfully employed in such efforts, yet these tests are often challenging to perform on fibers and come with certain limitations in the interpretation of the obtained results within the context of the macroscopic viscoelasticity in the fiber. Here we instead explore the properties of a series of natural and synthetic fibers, using a freely-oscillating torsional pendulum. The torsional oscillation of the damped mass-fiber system is precisely recorded with a simple HD video-camera and an image processing algorithm is used to analyze the resulting videos. Analysis of the processed images show a viscoelastic damped oscillatory response and a simple mechanical model describes the amplitude decay of the oscillation data very well. The natural frequency of the oscillation and the corresponding damping ratio can be extracted using a logarithmic decrement method and directly connected to the bulk viscoelastic properties of the fiber. We further study the sensitivity of these measurements to changes in the chemo-mechanical properties of the outer coating layers on one of the synthetic fibers. To quantify the accuracy of our measurements with the torsional pendulum, a complementary series of tests are also performed on a strain-controlled rheometer in both torsional and tensile deformation modes.

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Colloidal gels result from the aggregation of Brownian particles suspended in a solvent. Gelation is induced by attractive interactions between individual particles that drive the formation of clusters, which in turn aggregate to form a space-spanning structure. We study this process in aluminosilicate colloidal gels through time-resolved structural and mechanical spectroscopy. Using the time-connectivity superposition principle a series of rapidly acquired linear viscoelastic spectra, measured throughout the gelation process by applying an exponential chirp protocol, are rescaled onto a universal master curve that spans over eight orders of magnitude in reduced frequency. This analysis reveals that the underlying relaxation time spectrum of the colloidal gel is symmetric in time with power-law tails characterized by a single exponent that is set at the gel point. The microstructural mechanical network has a dual character; at short length scales and fast times it appears glassy, whereas at longer times and larger scales it is gel-like. These results can be captured by a simple three-parameter constitutive model and demonstrate that the microstructure of a mature colloidal gel bears the residual skeleton of the original sample-spanning network that is created at the gel point. Our conclusions are confirmed by applying the same technique to another well-known colloidal gel system composed of attractive silica nanoparticles. The results illustrate the power of the time-connectivity superposition principle for this class of soft glassy materials and provide a compact description for the dichotomous viscoelastic nature of weak colloidal gels.

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In recent years, researchers have incorporated mussel-inspired metal-coordinate cross-links into various types of gels to improve their mechanical properties, particularly toughness and self-healing. However, not much is understood about how the linear mechanical properties of these gels dictate their tack properties. In this study, we use shear rheology and tack tests to explore correlations between linear viscoelastic properties (i.e., plateau modulus, Gp, and characteristic relaxation time, τc) and tack behavior (i.e., peak stress, σmax, and energy dissipation per volume, EDV) of transiently cross-linked hydrogels comprised of histidine-functionalized 4-arm PEG coordinated with Ni2+. By using the Ni2+-histidine ratio and polymer wt % of the transient networks to control their viscoelastic properties, we demonstrate a strong dependence of σmax on Gp and τc. The observed correlation between network dynamics and mechanics under tensile load is in good quantitative agreement with a theoretical framework for σmax, which includes the linear viscoelastic properties as parameters. EDV is also influenced by Gp and τc, and the EDV after reaching σmax is additionally dependent on the polymer wt %. These findings are consistent with previously proposed molecular mechanics of reversible HisxNi2+ cross-links and provide us with new insights into the correlations between bulk mechanics and adhesive dynamics of gels with transient metal-coordinate cross-links.

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Biominerals have been widely studied due to their unique mechanical properties, afforded by their inorganic-organic composite structure and well-controlled growth in macromolecular environments. However, a lack of suitable characterization techniques for inorganic minerals in organic-rich media has prevented a full understanding of biomineralization. Here, we applied rheometry to study mineral nucleation and growth dynamics by measuring viscoelastic material properties of a hydrogel system during mineralization. Our proof-of-concept system consists of a gelatin hydrogel matrix preloaded with calcium ions and a reservoir of carbonate ions, which diffuse through the gel to initiate mineralization. We found that gels with diffused carbonate show an increase in low frequency energy dissipation, which scales with carbonate concentration and gel pH. Using this signal, and recognizing that mineralization occurs simultaneously with carbonate diffusion in our system, we have mechanoscopically tracked mineral growth in situ, showcasing the potential of rheometry for studying mineralization kinetics in real time.

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Polymer gels behave as soft viscoelastic solids and exhibit a generic nonlinear mechanical response characterized by pronounced stiffening prior to irreversible failure, most often through macroscopic fractures. Here, we describe this scenario for a model protein gel using an integral constitutive equation built upon the linear and the nonlinear viscoelastic properties of the gel. We show that this formalism predicts quantitatively the gel mechanical response in shear start-up experiments, up to the onset of macroscopic failure. Moreover, we couple the computed stress response with Bailey's durability criterion for brittle solids in order to predict the critical values of the stress σc and strain γc at failure. The excellent agreement between theory and experiments suggests that failure in this soft viscoelastic gel is a Markovian process and that Bailey's failure criterion extends beyond hard materials such as metals, glasses, or minerals.

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The breakup and atomization of complex fluids can be markedly different than the analogous processes in a simple Newtonian fluid. Atomization of paint, combustion of fuels containing antimisting agents, as well as physiological processes such as sneezing are common examples in which the atomized liquid contains synthetic or biological macromolecules that result in viscoelastic fluid characteristics. Here, we investigate the ligament-mediated fragmentation dynamics of viscoelastic fluids in three different canonical flows. The size distributions measured in each viscoelastic fragmentation process show a systematic broadening from the Newtonian solvent. In each case, the droplet sizes are well described by Gamma distributions which correspond to a fragmentation-coalescence scenario. We use a prototypical axial step strain experiment together with high-speed video imaging to show that this broadening results from the pronounced change in the corrugated shape of viscoelastic ligaments as they separate from the liquid core. These corrugations saturate in amplitude and the measured distributions for viscoelastic liquids in each process are given by a universal probability density function, corresponding to a Gamma distribution with n_{min}=4. The breadth of this size distribution for viscoelastic filaments is shown to be constrained by a geometrical limit which can not be exceeded in ligament-mediated fragmentation phenomena.

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Understanding the elongational rheology of dilute polymer solutions plays an important role in many biological and industrial applications ranging from microfluidic lab-on-a-chip diagnostics to phenomena such as fuel atomization and combustion. Making quantitative measurements of the extensional viscosity for dilute viscoelastic fluids is a long-standing challenge and it motivates developments in microfluidic fabrication techniques and high speed/strobe imaging of millifluidic capillary phenomena in order to develop new classes of instruments. In this paper, we study the elongational rheology of a family of dilute polymeric solutions in two devices: first, steady pressure-driven flow through a hyperbolic microfluidic contraction/expansion and, second, the capillary driven breakup of a thin filament formed from a small diameter jet ([Formula: see text]). The small length scale of the device allows very large deformation rates to be achieved. Our results show that in certain limits of low viscosity and elasticity, jet breakup studies offer significant advantages over the hyperbolic channel measurements despite the more complex implementation. Using our results, together with scaling estimates of the competing viscous, elastic, inertial and capillary timescales that control the dynamics, we construct a dimensionless map or nomogram summarizing the operating space for each instrument.

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A controlled synthesis of polymeric particles is becoming increasingly important because of emerging applications ranging from medical diagnostics to self-assembly. Centrifugal synthesis of hydrogel microparticles is a promising method, combining rapid particle synthesis and the ease of manufacturing with readily available laboratory equipment. This method utilizes centrifugal forces to extrude an aqueous polymer solution, sodium alginate (NaALG) through a nozzle. The extruded solution forms droplets that quickly cross-link upon contact with aqueous calcium chloride (CaCl2) solution to form hydrogel particles. The size distribution of hydrogel particles is dictated by the pinch-off behavior of the extruded solution through a balance of inertial, viscous, and surface tension stresses. We identify the parameters dictating the particle size and provide a numerical correlation predicting the average particle size. Furthermore, we create a phase map identifying different pinch-off regimes (dripping without satellites, dripping with satellites, and jetting), explaining the corresponding particle size distributions, and present scaling arguments predicting the transition between regimes. By shedding light on the underlying physics, this study enables the rational design and operation of particle synthesis by centrifugal forces.

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When a drop impacts a thin fiber, a critical impact speed can be defined, below which the drop is entirely captured by the fiber, and above which the drop pinches-off and fractures. We discuss here the capture dynamics of both inviscid and viscous drops on flexible fibers free to deform following impact. We characterize the impact-induced elongation of the drop thread for both high and low viscosity drops, and show that the capture dynamics depends on the relative magnitudes of the bending time of the fiber and deformation time of the drop. In particular, when these two timescales are comparable, drop capture is less prevalent, since the fiber rebounds when the drop deformation is maximal. Conversely, larger elasticity and slower bending time favor drop capture, as fiber rebound happens only after the drop has started to recoil. Finally, in the limit of highly flexible fibers, drop capture depends solely on the relative speed between the drop and the fiber directly after impact, as is prescribed by the momentum transferred during impact. Because the fiber speed directly after impact decreases with increasing fiber length and fiber mass, our study identifies an optimal fiber length for maximizing the efficiency of droplet capture.

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Cellulose derivatives containing associating hydrophobic groups along their hydrophilic backbone are used as rheology modifiers in the formulation of water-based spray paints, medicinal sprays, cosmetics and printable inks. Jetting and spraying applications of these materials involve progressive thinning and break-up of a fluid column or sheet into drops. Strong extensional kinematics develop in the thinning fluid neck. In viscous Newtonian fluids, inertial and viscous stresses oppose the surface tension-driven instability. In aqueous solutions of polymers such as Ethyl Hydroxy-Ethyl Cellulose (EHEC), chain elongation provides additional elastic stresses that can delay the capillary-driven pinch-off, influencing the sprayability or jettability of the complex fluid. In this study, we quantify the transient response of thinning filaments of cellulose ether solutions to extensional flows in a Capillary Break-up Extensional Rheometer (CaBER) and in a forced jet undergoing break-up using Rayleigh Ohnesorge Jetting Extensional Rheometry (ROJER). We also characterize the steady state molecular deformations using measurements of the flow-induced birefringence and excess pressure drop in an extensional stagnation point flow using a Cross-Slot Extensional Rheometer (CSER). We show that under the high extension rates encountered in jetting and spraying, the semi-dilute solutions of hydrophobically modified ethyl hydroxy-ethyl cellulose (hmEHEC) exhibit extensional thinning, while the unmodified bare chains of EHEC display an increase in extensional viscosity, up to a plateau value. For both EHEC and hmEHEC dispersions, the low extensibility of the cellulose derivatives limits the Trouton ratio observed at the highest extension rates attained (close to 10(5) s(-1)) to around 10-20. The reduction in extensional viscosity with increasing extension rate for the hydrophobically modified cellulose ether is primarily caused by the disruption of a transient elastic network that is initially formed by intermolecular association of hydrophobic stickers. This extensional thinning behavior, in conjunction with the low extensibility of the hydrophobically modified cellulose ether additives, makes these rheology modifiers ideal for controlling the extensional rheology in formulations that require jetting or spraying, with minimal residual stringiness or stranding.