Capillary break-up rheometry of low-viscosity elastic fluids

We investigate the dynamics of the capillary thinning and break-up process for low viscosity elastic fluids such as dilute polymer solutions. Standard measurements of the evolution of the midpoint diameter of the necking fluid filament are augmented by high speed digital video images of the break up dynamics. We show that the successful operation of a capillary thinning device is governed by three important time scales (which characterize the relative importance of inertial, viscous and elastic processes), and also by two important length scales (which specify the initial sample size and the total stretch imposed on the sample). By optimizing the ranges of these geometric parameters, we are able to measure characteristic time scales for tensile stress growth as small as 1 millisecond for a number of model dilute and semi-dilute solutions of polyethylene oxide (PEO) in water and glycerol. If the final aspect ratio of the sample is too small, or the total axial stretch is too great, measurements are limited, respectively, by inertial oscillations of the liquid bridge or by the development of the well-known beads-on-a-string morphology which disrupt the formation of a uniform necking filament. By considering the magnitudes of the natural time scales associated with viscous flow, elastic stress growth and inertial oscillations it is possible to construct an operability diagram characterizing successful operation of a capillary break-up extensional rheometer. For Newtonian fluids, viscosities greater than approximately 70 mPas are required; however for dilute solutions of high molecular weight polymer, the minimum Viscosity is substantially lower due to the additional elastic stresses arising from molecular extension. For PEO of molecular weight 2.10(6) g/mol, it is possible to measure relaxation times of order 1 ms in dilute polymer solutions with zero-shear-rate viscosities on the order of 2-10 mPas.

Microfluidic Rheometry

The development and growth of microfluidics has stimulated interest in the behaviour of complex liquids in micro-scale geometries and provided a rich platform for rheometric investigations of non-Newtonian phenomena at small scales. Microfluidic techniques present the rheologist with new opportunities for material property measurement and this review discusses the use of microfluidic devices to measure bulk rheology in both shear and extensional flows. Capillary, stagnation and contraction flows are presented in this context and developments, limitations and future perspectives are examined. (C) 2008 Elsevier Ltd. All rights reserved.

The competing roles of extensional viscosity and normal stress differences in complex flows of elastic liquids

In various attempts to relate the behaviour of highly-elastic liquids in complex flows to their rheometrical behaviour, obvious candidates for study have been the variation of shear viscosity with shear rate, the two normal stress differences N(1) and N(2) especially N(1), and the extensional viscosity eta(E). In this paper, we shall be mainly interested in `constant-viscosity` Boger fluids, and, accordingly, we shall limit attention to N(1) and eta(E). We shall concentrate on two important flows - axisymmetric contraction flow and ""splashing"" (particularly that which arises when a liquid drop falls onto the free Surface of the same liquid). Modem numerical techniques are employed to provide the theoretical predictions. It is shown that the two obvious manifestations of viscoelastic rheometrical behaviour can sometimes be opposing influences in determining flow characteristics. Specifically, in an axisymmetric contraction flow, high eta(E) , can retard the flow, whereas high N(1) can have the opposite effect. In the splashing experiment, high eta(E) can certainly reduce the height of the so-called Worthington jet, thus confirming some early suggestions, but, again, other rheometrical influences can also have a role to play and the overall picture may not be as clear as it was once envisaged.

25 million years to break a continent : early to middle Miocene rifting and syn-extensional magmatism in the southern Gulf of California

Cenozoic extension in western Mexico has been divided into two episodes separated by the change from convergence to oblique divergence at the plate boundary. The Gulf Extensional Province is thought to have started once subduction ended at ~12.5 Ma whereas early extension is classified as Basin and Range. Mid-Miocene volcanism of the Comondú group has been considered as a subduction-related arc, whereas post ~12.5 Ma volcanism would be extension-related. Our new integration of the continental onshore and offshore geology of the south-east Gulf region, backed by tens of Ar-Ar and U-Pb ages and geochemical studies, document an early-mid Miocene rifting and extension-related bimodal to andesitic magmatism prior to subduction termination. Between ~21 and 11 Ma a system of NNW-SSE high-angle extensional faults rifted the western side of the Sierra Madre Occidental (SMO) ignimbrite plateau. In Nayarit, rhyolitic domes and some basalts were emplaced along this extensional belt at 18-17 Ma. These rocks show strong antecrystic inheritance but an absence of Mesozoic and older xenocrysts, suggesting a genesis in the mid-upper crust triggered by extension-induced basaltic influx. In Sinaloa, large grabens were floored by huge dome complexes at ~21-17 Ma and filled by continental sediments with interlayered basalts dated at 15 Ma. Mid-Miocene volcanism, including the largely volcaniclastic Comondú strata in Baja California, was thus emplaced in rift basins and appears associated to decompression melting rather than subduction. Along the coast, flat-lying basaltic lava flows dated at 11-10 Ma are exposed just above the present sea level. Here crustal thickness is 25-20 Km, almost half that in the core of the SMO, implying significant lithosphere stretching before ~11 Ma. This mafic pulse, with relatively high Ti but still clear Nb-Ta negative spikes, may be related to the detachment of the lower part of the subducted slab, allowing asthenosphere to flow into parts of the mantle previously fluxed by subduction fluids. Very uniform OIB-like lavas appear in late Pliocene and Pleistocene, only 18 m.y. after the onset of rifting and ~9 m.y. after the end of subduction. Our study shows that rifting began much earlier than Late Miocene and progressively overwhelmed subduction in generating magmatism.

Late Oligocene to middle Miocene rifting and syn-extensional magmatism in the southwestern Sierra Madre occidental, Mexico: the beginning of the Gulf of California rift

Although Basin and Range style extension affected several areas of western Mexico since the Late Eocene, extension in the Gulf of California region (the Gulf Extensional Province GEP) is thought to have started as subduction waned and ended at ~14 12.5 Ma. A general consensus also exists in considering the mid Miocene Comondú group as a suprasubduction volcanic arc. Our new integration of the geology of the south east Gulf region, backed by 43 new Ar Ar and U Pb mineral ages and geochemical studies, document a widespread phase of extension in the southern GEP between latest Oligocene and Early Miocene that subsequently focused in the region of the future Gulf in the Middle Miocene. Upper Oligocene to Lower Miocene rocks across the southern Sierra Madre Occidental (SMO)(northern Nayarit and southern Sinaloa) were affected by major ~N S to NNW striking normal faults prior to ~21 Ma. Then, between ~21 and 11 Ma, a system of NNW-SSE high angle extensional faults continued extending the southwestern side of the SMO. Rhyolitic domes, shallow intrusive bodies, and lesser basalts were emplaced along this extensional belt at 20-17 Ma. In northern Sinaloa, large grabens were floored by huge dome complexes at ~21-17 Ma and filled by continental sediments with interlayered basalts dated at 15-14 Ma, a setting and timing very similar to Sonora. Early to Middle Miocene volcanism, including the largely volcaniclastic Comondú strata in Baja California Sur, was thus emplaced in rift basins and was likely associated to decompression melting of upper mantle (inducing crustal partial melting) rather than to fluxing by fluids from the young subducting plate. Along the Nayarit and Sinaloa coast, flatlying basaltic lava flows dated at 11-10 Ma are exposed just above the present sea level. Here, crustal thickness is almost half that in the unextended core of the SMO, implying significant lithosphere stretching before ~11 Ma. Our study shows that rifting began much earlier than Late Miocene and provided a fundamental control on the style and composition of volcanism from at least 30 Ma. We envision a sustained period of lithospheric stretching and magmatism during which the pace and breadth of extension changed at ~20-18 Ma to be narrower and likely more rapid, and again at ~12.5 Ma, when the kinematics of rifting became more oblique.

Consequences of extensional tectonics on volcanic eruption style, compositions and source regions : new insights from the southern Sierra Madre Occidental and Gulf of California regions, western Mexico

Understanding the link between tectonic-driven extensional faulting and volcanism is crucial from a hazard perspective in active volcanic environments, while ancient volcanic successions provide records on how volcanic eruption styles, compositions, magnitudes and frequencies can change in response to extension timing, distribution and intensity. This study draws on intimate relationships of volcanism and extension preserved in the Sierra Madre Occidental (SMO) and Gulf of California (GoC) regions of western Mexico. Here, a major Oligocene rhyolitic ignimbrite “flare-up” (>300,000 km3) switched to a dominantly bimodal and mixed effusive-explosive volcanic phase in the Early Miocene (~100,000 km3), associated with distributed extension and opening of numerous grabens. Rhyolitic dome fields were emplaced along graben edges and at intersections of cross-graben and graben-parallel structures during early stages of graben development. Concomitant with this change in rhyolite eruption style was a change in crustal source as revealed by zircon chronochemistry with rapid rates of rhyolite magma generation due to remelting of mid- to upper crustal, highly differentiated igneous rocks emplaced during earlier SMO magmatism. Extension became more focused ~18 Ma resulting in volcanic activity being localised along the site of GoC opening. This localised volcanism (known as the Comondú “arc”) was dominantly effusive and andesite-dacite in composition. This compositional change resulted from increased mixing of basaltic and rhyolitic magmas rather than fluid flux melting of the mantle wedge above the subducting Guadalupe Plate. A poor understanding of space-time relationships of volcanism and extension has thus led to incorrect past tectonic interpretations of Comondú-age volcanism.

Mechanistic overview of the curing behavior of hydride terminated polydimethylsiloxane with allyl functionalized alumina by calorimetry and rheometry

The study of the curing behavior of an encapsulation material is very important and critical in terms of understanding the properties of the material. Differential scanning calorimetry and rheometry are two important tools that have been utilized to study curing reactions in polymeric systems. The present work deals with the curing of a mixture of hydride terminated polydimethylsiloxane, allyl functionalized alumina nanoparticles and Karstedt's catalyst. The real time curing behavior of the typical system was monitored non-isothermally by differential scanning calorimetry and rheometry. The results obtained from the respective techniques reveal that there is a good correlation between these two techniques. A mechanism is proposed for the curing reaction of the polymer system based on the curing curves obtained by the above two studies. In addition, the swelling study and contact angle measurement of the two composites was performed to evaluate the extent of cross-linking and hydrophobicity. (C) 2011 Elsevier B.V. All rights reserved.

Rheometry of dense granular materials: the crucial effects of gravity and confining walls

We describe here the rheological response of dense, slowly deforming granular materials to shear in a cylindrical Couette cell. All components of the stress on the outer cylinder are measured pointwise as a function of the depth, for different methods of construction of the bed that presumably lead to distinct fabrics. The static stress profiles for the different construction protocols are different, but a stress profile that is independent of construction history emerges when the granular column is sheared for sufficient time, in accord with the predictions of plasticity theories. However the qualitative features of the the stress profile under shear differs radically from the predictions of plasticity theories and data reported in earlier studies. We discuss a hypothesis for the anomalous stress profiles that was proposed recently by us, and the ways in which further experiments may to conducted to verify it.

Rheometry of granular materials in cylindrical Couette cells: Anomalous stress caused by gravity and shear

The cylindrical Couette device is commonly employed to study the rheology of fluids, but seldom used for dense granular materials. Plasticity theories used for granular flows predict a stress field that is independent of the shear rate, but otherwise similar to that in fluids. In this paper we report detailed measurements of the stress as a function of depth, and show that the stress profile differs fundamentally from that of fluids, from the predictions of plasticity theories, and from intuitive expectation. In the static state, a part of the weight of the material is transferred to the walls by a downward vertical shear stress, bringing about the well-known Janssen saturation of the stress in vertical columns. When the material is sheared, the vertical shear stress changes sign, and the magnitudes of all components of the stress rise rapidly with depth. These qualitative features are preserved over a range of the Couette gap and shear rate, for smooth and rough walls and two model granular materials. To explain the anomalous rheological response, we consider some hypotheses that seem plausibleapriori, but showthat none survive after careful analysis of the experimental observations. We argue that the anomalous stress is due to an anisotropic fabric caused by the combined actions of gravity, shear, and frictional walls, for which we present indirect evidence from our experiments. A general theoretical framework for anisotropic plasticity is then presented. The detailed mechanics of how an anisotropic fabric is brought about by the above-mentioned factors is not clear, and promises to be a challenging problem for future investigations. (C) 2013 AIP Publishing LLC.

The mixing of bubbles in two-dimensional bidisperse foams under extensional shear

Cox, S.J. (2006) The mixing of bubbles in two-dimensional bidisperse foams under extensional shear. Journal of Non-Newtonian Fluid Mechanics . 137:39-45.

Characterisation of the Interaction of Lactate Dehydrogenase With Tween-20 Using Isothermal Titration Calorimetry, Interfacial Rheometry and Surface Tension Measurements

In this study the nature of the interaction between Tween-20 and lactate dehydrogenase (LDH) was investigated using isothermal titration calorimetry (ITC). In addition the effects of the protein and surfactant on the interfacial properties were followed with interfacial rheology and surface tension measurements in order to understand the mechanism by which the surfactant prevents protein adsorption to the air– water interface. Comparisons were made with Tween-40 and Tween-80 in order to further investigate the mechanism. ITC measurements indicated a weak, probably hydrophobic, interaction between Tween-20 and LDH. Prevention of LDH adsorption to the air–water interface by the Tween surfactants was correlated with surface energy rather than surfactant CMC. While surface pressure appears to be the main driving force for the displacement of LDH from the air–water interface by Tween-20 a solubilisation mechanism may exist for other protein molecules. More generally the results of this study highlight the value of the use of ITC and interfacial measurements in characterising the surface behaviour of mixed surfactant and protein systems.

Textural analysis and flow rheometry of novel, bioadhesive antimicrobial oral gels

Purpose. This study examined the rheological and textural characteristics (hardness, compressibilty, adhesiveness and cohesiveness) of bioadhesive oral gels containing the antimicrobial agent chlorhexidine.

Characterization and structure–property relationship of melt-mixed high density polyethylene/multi-walled carbon nanotube composites under extensional deformation

Melt-mixed high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites with 1–10 wt% MWCNTs were prepared by twin screw extrusion and compression moulded into sheet form. The compression moulded nanocomposites exhibit a 112% increase in modulus at a MWCNT loading of 4 wt%, and a low electrical percolation threshold of 1.9 wt%. Subsequently, uniaxial, sequential (seq-) biaxial and simultaneous (sim-) biaxial stretching of the virgin HDPE and nanocomposite sheets was conducted at different strain rates and stretching temperatures to investigate the processability of HDPE with the addition of nanotubes and the influence of deformation on the structure and final properties of nanocomposites. The results show that the processability of HDPE is improved under all the uniaxial and biaxial deformation conditions due to a strengthened strain hardening behaviour with the addition of MWCNTs. Extensional deformation is observed to disentangle nanotube agglomerates and the disentanglement degree is shown to depend on the stretching mode, strain rate and stretching temperatures applied. The disentanglement effectiveness is: uniaxial stretching < sim-biaxial stretching < seq-biaxial stretching, under the same deformation parameters. In sim-biaxial stretching, reducing the strain rate and stretching temperature can lead to more nanotube agglomerate breakup. Enhanced nanotube agglomerate disentanglement exhibits a positive effect on the mechanical properties and a negative effect on the electrical properties of the deformed nanocomposites. The ultimate stress of the composite containing 4 wt% MWCNTs increased by ∼492% after seq-biaxial stretching, while the resistivity increased by ∼1012 Ω cm.

Characterisation and modelling of the thermorheological properties of pharmaceutical polymers and their blends using capillary rheometry: Implications for hot melt processing of dosage forms.

Given the growing interest in thermal processing methods, this study describes the use of an advanced rheological technique, capillary rheometry, to accurately determine the thermorheological properties of two pharmaceutical polymers, Eudragit E100 (E100) and hydroxypropylcellulose JF (HPC) and their blends, both in the presence and absence of a model therapeutic agent (quinine, as the base and hydrochloride salt). Furthermore, the glass transition temperatures (Tg) of the cooled extrudates produced using capillary rheometry were characterised using Dynamic Mechanical Thermal Analysis (DMTA) thereby enabling correlations to be drawn between the information derived from capillary rheometry and the glass transition properties of the extrudates. The shear viscosities of E100 and HPC (and their blends) decreased as functions of increasing temperature and shear rates, with the shear viscosity of E100 being significantly greater than that of HPC at all temperatures and shear rates. All platforms were readily processed at shear rates relevant to extrusion (approximately 200–300 s−1) and injection moulding (approximately 900 s−1). Quinine base was observed to lower the shear viscosities of E100 and E100/HPC blends during processing and the Tg of extrudates, indicative of plasticisation at processing temperatures and when cooled (i.e. in the solid state). Quinine hydrochloride (20% w/w) increased the shear viscosities of E100 and HPC and their blends during processing and did not affect the Tg of the parent polymer. However, the shear viscosities of these systems were not prohibitive to processing at shear rates relevant to extrusion and injection moulding. As the ratio of E100:HPC increased within the polymer blends the effects of quinine base on the lowering of both shear viscosity and Tg of the polymer blends increased, reflecting the greater solubility of quinine within E100. In conclusion, this study has highlighted the importance of capillary rheometry in identifying processing conditions, polymer miscibility and plasticisation phenomena.