Pendant drop formation of shear-thinning and yield stress fluids

A volume-of-fluid numerical method is used to predict the dynamics of shear-thinning liquid drop formation in air from a circular orifice. The validity of the numerical calculation is confirmed for a Newtonian liquid by comparison with experimental measurements. For particular values of Weber number and Froude number, predictions show a more rapid pinch-off, and a reduced number of secondary droplets, with increasing shear-thinning. Also a minimum in the limiting drop length occurs for the smallest Weber number as the zero-shear viscosity is varied. At the highest viscosity, the drop length is reduced due to shear-thinning, whereas at lower viscosities there is little effect of shear-thinning. The evolution of predicted drop shape, drop thickness and length, and the configuration at pinch-off are discussed for shear-thinning drops. The evolution of a drop of Bingham yield stress liquid is also considered as a limiting case. In contrast to the shear-thinning cases, it exhibits a plug flow prior to necking, an almost step-change approach to pinch-off of a torpedo shaped drop following the onset of necking, and a much smaller neck length; no secondary drops are formed. The results demonstrate the potential of the numerical model as a design tool in tailoring the fluid rheology for controlling drop formation behaviour. (c) 2006 Elsevier Inc. All rights reserved.

Simulations of pendant drop formation of a viscoelastic liquid

A modified Volume-of-Fluid (VOF) numerical method is used to predict the dynamics of a liquid drop of a low viscosity dilute polymer solution, forming in air from a circular nozzle. Viscoelastic effects are represented using an Oldroyd-B model. Predicted drop shapes are compared with experimental observations. The main features, including the timing of the shape evolution and the bead-on-a-string effect, are well reproduced by the simulations. The results confirm published conclusions of the third author, that the deformation is effectively Newtonian until near the time of Newtonian pinch-off and that the elastic stress becomes large in the pinch region due to the higher extensional flow there.

Three classes of starch granule swelling: Influence of surface proteins and lipids

The role of non-carbohydrate surface components of granular starch in determining gelatinisation behaviour has been tested by treatment of native starches with a range of extractants. Resulting washed starches were analysed for (bio)chemical, calorimetric and theological properties. Sodium dodecyl sulphate (SDS) was the most efficient extractant tested, and resulted in major changes to the subsequent theological properties of wheat and maize starches but not other starches. Three classes of starch granule swelling behaviour are identified: (i) rapid swelling (e.g. waxy maize, potato), (ii) slow swelling that can be converted to rapid swelling by extraction of surface proteins and lipids (e.g. wheat, maize), and (iii) limited swelling not affected by protein/lipid extraction (e.g. high amylose maize/potato). Comparison of a range of extractants suggests that all of protein, lipid and amylose are involved in restriction of swelling for wheat or maize starches. Treatment of starches with SDS leads to a residue at comparable (low) levels of SDS for all starches. C-13 NMR analysis shows that this SDS is present as a glucan inclusion complex, even for waxy maize starch. We infer that under the conditions used, glucan inclusion complexation of SDS is equally likely with amylopectin as with amylose. (c) 2006 Elsevier Ltd. All rights reserved.

An anisotropic viscous representation of Mohr-Coulomb failure for use is modelling coupled mantle-continent dynamics

In mantle convection models it has become common to make use of a modified (pressure sensitive, Boussinesq) von Mises yield criterion to limit the maximum stress the lithosphere can support. This approach allows the viscous, cool thermal boundary layer to deform in a relatively plate-like mode even in a fully Eulerian representation. In large-scale models with embedded continental crust where the mobile boundary layer represents the oceanic lithosphere, the von Mises yield criterion for the oceans ensures that the continents experience a realistic broad-scale stress regime. In detailed models of crustal deformation it is, however, more appropriate to choose a Mohr-Coulomb yield criterion based upon the idea that frictional slip occurs on whichever one of many randomly oriented planes happens to be favorably oriented with respect to the stress field. As coupled crust/mantle models become more sophisticated it is important to be able to use whichever failure model is appropriate to a given part of the system. We have therefore developed a way to represent Mohr-Coulomb failure within a code which is suited to mantle convection problems coupled to large-scale crustal deformation. Our approach uses an orthotropic viscous rheology (a different viscosity for pure shear to that for simple shear) to define a prefered plane for slip to occur given the local stress field. The simple-shear viscosity and the deformation can then be iterated to ensure that the yield criterion is always satisfied. We again assume the Boussinesq approximation - neglecting any effect of dilatancy on the stress field. An additional criterion is required to ensure that deformation occurs along the plane aligned with maximum shear strain-rate rather than the perpendicular plane which is formally equivalent in any symmetric formulation. It is also important to allow strain-weakening of the material. The material should remember both the accumulated failure history and the direction of failure. We have included this capacity in a Lagrangian-Integration-point finite element code and will show a number of examples of extension and compression of a crustal block with a Mohr-Coulomb failure criterion, and comparisons between mantle convection models using the von Mises versus the Mohr-Coulomb yield criteria. The formulation itself is general and applies to 2D and 3D problems, although it is somewhat more complicated to identify the slip plane in 3D.

The control of alkali silica reaction using blended cements

It has been previously established that alkali silica reaction (ASR) in concrete may be controlled by blending Portland cement with suitable hydraulic or pozzolanic materials. The controlling mechanism has been attributed to the dilution of the cement's alkali content and reduced mobility of ions in concrete's pore solution. In this project an attempt has been made to identify the factors which influence the relative importance of each mechanism in the overall suppression of the reaction by the use of blended cements. The relationship between the pore solution alkalinity and ASR was explored by the use of expansive mortar bars submerged in alkaline solutions of varying concentration. This technique enabled the blended cement's control over expansion to be assessed at given `pore solution' alkali concentrations. It was established that the cement blend, the concentration and quantity of alkali present in the pore solution were the factors which determined the rate and extent of ASR. The release of alkalis into solution by Portland cements of various alkali content was studied by analysis of pore solution samples expressed from mature specimens. The specification for avoiding ASR by alkali limitation, both by alkali content of cement and the total quantity of alkali were considered. The effect on the pore solution alkalinity when a range of Portland cements were blended with various replacement materials was measured. It was found that the relationship between the type of replacement material, its alkali content and that of the cement were the factors which primarily determined the extent of the pore solution alkali dilution effect. It was confirmed that salts of alkali metals of the kinds found as common concrete contaminants were able to increase the pore solution hydroxyl ion concentration significantly. The increase was limited by the finite anion complexing ability of the cement.

Use of colour image analysis for assessment of fire damaged concrete

The aim of this project was to carry out a fundamental study to assess the potential of colour image analysis for use in investigations of fire damaged concrete. This involved:(a) Quantification (rather than purely visual assessment) of colour change as an indicator of the thermal history of concrete.(b) Quantification of the nature and intensity of crack development as an indication of the thermal history of concrete, supporting and in addition to, colour change observations.(c) Further understanding of changes in the physical and chemical properties of aggregate and mortar matrix after heating.(d) An indication of the relationship between cracking and non-destructive methods of testing e.g. UPV or Schmidt hammer. Results showed that colour image analysis could be used to quantify the colour changes found when concrete is heated. Development of red colour coincided with significant reduction in compressive strength. Such measurements may be used to determine the thermal history of concrete by providing information regarding the temperature distribution that existed at the height of a fire. The actual colours observed depended on the types of cement and aggregate that were used to make the concrete. With some aggregates it may be more appropriate to only analyse the mortar matrix. Petrographic techniques may also be used to determine the nature and density of cracks developing at elevated temperatures and values of crack density correlate well with measurements of residual compressive strength. Small differences in crack density were observed with different cements and aggregates, although good correlations were always found with the residual compressive strength. Taken together these two techniques can provide further useful information for the evaluation of fire damaged concrete. This is especially so since petrographic analysis can also provide information on the quality of the original concrete such as cement content and water / cement ratio. Concretes made with blended cements tended to produce small differences in physical and chemical properties compared to those made with unblended cements. There is some evidence to suggest that a coarsening of pore structure in blended cements may lead to onset of cracking at lower temperatures. The use of DTA/TGA was of little use in assessing the thermal history of concrete made with blended cements. Corner spalling and sloughing off, as observed in columns, was effectively reproduced in tests on small scale specimens and the crack distributions measured. Relationships between compressive strength/cracking and non-destructive methods of testing are discussed and an outline procedure for site investigations of fire damaged concrete is described.

Technology of repair for corroded reinforced concrete

A number of factors relating to various methods of repair for chloride initiated corrosion damage of reinforced concrete have been studied. A novel methodology has been developed to facilitate the measurement of macro and micro-cell corrosion rates for steel electrodes embedded in mortar prisms containing a chloride gradient. The galvanic bar specimen comprised electrically isolatable segmental mild steel electrodes and was constructed such that macro-cell corrosion currents were determinable for a number of electrode combinations. From this, the conditions giving rise to an incipient anode were established. The influence of several reinforcement and substrate primer systems upon macro-cell corrosion, arising from an incipient anode, within a patch repair have been investigated. Measurements of electrochemical noise were made in order to investigate the suitability of the technique as an on-site means of assessing corrosion activity within chloride contaminated reinforced concrete. For this purpose the standard deviation of potential noise was compared to macro-cell galvanic current data and micro-cell corrosion intensity determined by linear polarisation. Hydroxyl ion pore solution analyses were carried out on mortar taken from cathodically protected specimens. These specimens, containing sodium chloride, were cathodically protected over a range of polarisation potentials. Measurement of the hydroxyl ion concentrations were made in order to examine the possibility of alkali-silica reactions initiated by cathodic protection of reinfored concrete. A range of mortars containing a variety of generic type additives were examined in order to establish their resistances to chloride ion diffusion. The effect of surfactant addition rate was investigated within a cement paste containing various dosages of naphthalene sulphonate.

The spalling of concrete in fires

The occurrence of spalling is a major factor in determining the fire resistance of concrete constructions. The apparently random occurrence of spalling has limited the development and application of fire resistance modelling for concrete structures. This Thesis describes an experimental investigation into the spalling of concrete on exposure to elevated temperatures. It has been shown that spalling may be categorised into four distinct types, aggregate spalling, corner spalling, surface spalling and explosive spalling. Aggregate spalling has been found to be a form of shear failure of aggregates local to the heated surface. The susceptibility of any particular concrete to aggregate spalling can be quantified from parameters which include the coefficients of thermal expansion of both the aggregate and the surrounding mortar, the size and thermal diffusivity of the aggregate and the rate of heating. Corner spalling, which is particularly significant for the fire resistance of concrete columns, is a result of concrete losing its tensile strength at elevated temperatures. Surface spalling is the result of excessive pore pressures within heated concrete. An empirical model has been developed to allow quantification of the pore pressures and a material failure model proposed. The dominant parameters are rate of heating, pore saturation and concrete permeability. Surface spalling may be alleviated by limiting pore pressure development and a number of methods to this end have been evaluated. Explosive spalling involves the catastrophic failure of a concrete element and may be caused by either of two distinct mechanisms. In the first instance, excessive pore pressures can cause explosive spalling, although the effect is limited principally to unloaded or relatively small specimens. A second cause of explosive spalling is where the superimposition of thermally induced stresses on applied load stresses exceed the concrete's strength.

Properties and performance of polymer modified cements and mortars

Polymer modified cements and mortars have become popular for use as patch repair materials. General evidence suggests that these materials offer considerable improvements compared to traditional mortars although the mechanisms for this are not fully understood. This work elucidates the factors which govern some properties and performance of different polymer systems. In view of the wide range of commercial systems available, investigations concentrated on the use of three of the most commonly available groups of polymers. These were: (1) Styrene Butadiene Rubber (SBR), (2) Acrylics and, (3) Ethylene Vinyl Acetates (EVA). The later two were in the form of both emulsions and redispersible powders. Experiments concentrated on: (1) Rheological behaviour of polymer modified cement pastes; (2) Workability of polymer modified mortars; (3) Influence of curing conditions on the pore size distribution and diffusion of chloride ions; (4) Bond strength of polymer modified cement and mortar patches; and (5) Microscopic examination and semi-quantitative analyses of the bulk and interfacial microstructures. The following main conclusions were reached: (1) The addition of polymer emulsions have a considerable influence on the workability of fresh cement pastes, the extent of this depending on the type of system used. (2) The rheological parameters of fresh polymer modified mortars can be established using a two-point workability test which may be used when comparing the properties of different systems at constant workability. (3) Curing conditions affect the properties of polymer modified systems and a wet/dry curing regime was essential for good adhesion of these materials to mortar substrates. (4) In contrast, the wet/dry curing regime resulted in a curing affected zone at the surface of patch materials. This can result in a much coarser pore structure and enhanced diffusion of e.g. chloride ions. (5) The microstructure of polymer modified systems was very different compared with the unmodified cement/mortar and varied depending on curing conditions.

Ionic and neutral hydrogels for dermal and ophthalmic applications

This thesis is concerned with the use of ionic and neutral hydrogels in dermal and ocular applications with particular reference to controlled release applications. The work consists of three interconnected themes.The first area of study is the use of skin adhesive bioelectrode hydrogels as ground plate electrodes for ophthalmic iontophoresis applications. The work provides a basis of understanding the relative contributions made by ionic monomers (such as sodium s-(acrylamide)-2-methyl propane sulphonate and acrylic acid-bis-(3-sulfopropyl-ester, potassium salt) and neutral monomers (such as acryloymorpholine, N,N-dimethylacrylamide and N-vinyl pyrrolidone) to adhesion, rheology and impedance of bioelectrode gels. The general advantage of neutral monomers, which have been used to successfully replace ionic monomers, is that they enable more effective control of independent anion and cation species (for example potassium chloride and sodium chloride) unlike ionic monomers where polymerisation produces an immobile polyanion thus limiting cation mobility. Secondly, release from a completely neutral hydrogel under the influence of mechanical shaking was studied for the case of crosslinked polyvinyl alcohol (PVA) containing low concentration of linear soluble PVA in a contact lens application. The soluble PVA was observed to be eluting by reptation from the lens matrix due to the mechanical action of the eyelid. This process was studied in an in vitro model, which in this research was used as a basis for developing a lens made with enhanced release polymer. The third area of work is related to the factors that control drug release (in particular non-steroidal anti-inflammatory drugs) from a hydrogel matrix. This links both electrotherapy applications, such as transcutaneous electrical nerve stimulation, in which the passive diffusion from the gel could be used in conjunction with enhanced transmission across the dermal surface with passive diffusion from a contact lens matrix and the development of therapeutic contact lenses.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.