Anomalous Viscosity Reduction and Hydrodynamic Interactions of Polymeric Nanocolloids in Polymers

One of the central dogmas of fluid physics is the no-slip boundary condition, whose validity has come under scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective viscosity experienced by polymeric nano colloids moving through a highly viscous and confined polymer, well above its glass transition temperature. The extent of reduction in effective interface viscosity increases with decreasing temperature and polymer film thickness. Concomitant with the reduction in effective viscosity we also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these colloids with an anomalous power law exponent of similar to 2 at the lowest temperatures and film thickness studied. Such strong hydrodynamic interactions are not expected for polymeric colloidal motion in polymer melts. We suggest hydrodynamics, especially slip present at the colloid-polymer interface which determines the observed reduction in interface viscosity and presence of strong hydrodynamic interactions.

Rheology, morphology and mechanical properties of LLDPE/PS blends catalyzed by combined Lewis acids

The rheological, morphological and mechanical properties of LLDPE/PS blends with a combined catalyst, Me3SiCl and InCl3 center dot 4H(2)O, were studied in this work. The higher complex viscosity and storage modulus at low frequency were ascribed to the presence of graft copolymers, which were in situ formed during the mixing process. From the rheological experiments, the complex viscosity and storage modulus of reactive blends were higher than the physical blends. The dispersion of LLDPE particles of reactive blending becomes finer than that of physical blends, consistent with the rheological results. As a result of increased compatibility between LLDPE/PS, the mechanical properties of reactive blends show much higher tensile and Izod impact strength than those of physical blends.

The rheological properties of polyaniline solution

This paper presents our work on the rheological properties of the solution of polyaniline (PAn) in N-methyl-2-pyrrolidone (NMP). The results indicate that the solution's non-Newtonian property becomes more prominent with the increase in solution concentrations exhibiting the behavior of pseudo-plastic fluid. Besides, there is a critical concentration C-v (around 0.06 g/ml), beyond which the viscosity of the PAn/NMP solution takes a sudden increase. with temperature rising, both the viscosity and the thixotropy of the solution decrease, implying that there exist physical cross-linking interactions between the molecular chains in the solution.

The effect of wall-slip formation on the rheological behaviour of lead-free solder pastes

Wall-slip plays an important role in the flow behaviour of solder paste materials. The wall-slip arises due to the various attractive and repulsive forces acting between the solder particles and the walls of the measuring geometry. These interactions could lead to the presence of a thin liquid layer adjacent to the wall, which causes slippage. The aim of this study is to investigate the influence of the solder paste formulation on wall-slip formation and its effect on the printability of these pastes material. A wall slip model is utilised to calculate the true viscosity and slip velocity for the lead-free solder pastes samples used in this study. The difference in the measured viscosity and the true viscosity could indicate wall-slip formation between the solder pastes and the parallel plate. Sample P1 showed a higher slip velocity compared to sample P2. The slip velocity calculated for the solder pastes could be used as a performance indicator to understand the paste release characteristics in the stencil printing process.

Formulation and characterisation of tetracycline-containing bioadhesive polymer networks designed for the treatment of periodontal disease.

This study described the drug release, rheological (dynamic and flow) and textural/mechanical properties of a series of formulations composed of 15% w/w polymethylvinylether-co-maleic anhydride (PMVE-MA), 0-9% w/w polyvinylpyrrolidone (PVP) and containing 1-5% w/w tetracycline hydrochloride, designed for the treatment of periodontal disease. All formulations exhibited pseudoplastic flow with minimal thixotropy. Increasing the concentration of PVP sequentially increased the zero-rate viscosity (derived from the Cross model) and the hardness and compressibility of the formulations (derived from texture profile analysis). These affects may be accredited to increased polymer entanglement and, in light of the observed synergy between the two polymers with respect to their textural and rheological properties, interaction between PVP and PMVE-MA. Increasing the concentration of PVP increased the storage and loss moduli yet decreased the loss tangent of all formulations, indicative of increased elastic behaviour. Synergy between the two polymers with respect to their viscoelastic properties was observed. Increased adhesiveness, associated with increased concentrations of PVP was ascribed to the increasing bioadhesion and tack of the formulations. The effect of increasing drug concentration on the rheological and textural properties was dependent on PVP concentration. At lower concentrations (0, 3% w/w) no effect was observed whereas, in the presence of 9% w/w PVP, increasing drug concentration increased formulation elasticity, zero rate viscosity, hardness and compressibility. These observations were ascribed to the greater mass of suspended drug in formulations containing the highest concentration of PVP. Drug release from formulations containing 6 and 9% PVP (and 5% w/w drug) was prolonged and swelling/diffusion controlled. Based on the drug release, rheological and textural properties, it is suggested that the formulation containing 15% w/w PMVE-MA, 6% w/w PVP and tetracycline hydrochloride (5% w/w) may be useful for the treatment of periodontal disease.

Polymer conditioning of alum sludge and discrepancies between estimates of the optimum dosage

The paper outlines the effects of polymer conditioning on alum sludge properties, such as floc size, density, fractal dimension (DF) and rheological properties. Experimental results demonstrate that polymer conditioning of alum sludge leads to: larger floc size with a plateau reached in higher doses; higher densities associated with higher doses; increased degree of compactness; and an initial decrease followed by an increase of supernatant viscosity with continued increase in polymer dose. The secondary focus of this paper dwells on a comparison of the estimates of optimum dose using different criteria that emanate from established dewatering tests such as CST, SRF, liquid phase viscosity and modified SRF as well as a simple settlement test in terms of CML30. Alum sludge was derived from a water works treating coloured, low-turbidity raw waters.

Separate Density and Viscosity Determination of Room Temperature Ionic Liquids using Dual Quartz Crystal Microbalances

The drive towards cleaner industrial processes has led to the development of room temperature ionic liquids (RTIL) as environmentally friendly solvents. They comprise solely of ions which are liquid at room temperature and with over one million simple RTIL alone it is important to characterize their physical properties using minimal sample volumes. Here we present a dual Quartz Crystal Microbalance (QCM) which allows separate determination of viscosity and density using a total sample volume of only 240 mu L. Liquid traps were fabricated on the sensing area of one QCM using SU-8 10 polymer with a second QCM having a flat surface. Changes in the resonant frequencies were used to extract separate values for viscosity and density. Measurements of a range of pure RTIL with minimal water content have been made on five different trap designs. The best agreement with measurements from the larger volume techniques was obtained for trap widths of around 50 pm thus opening up the possibility of integration into lab-on-a-chip systems.

Effect of Nanosilica on Rheology, Fresh Properties, and Strength of Cement-Based Grouts

The effect of colloidal nanosilica on the fresh and rheological parameters, plastic shrinkage, heat of hydration, and compressive strength of cement-based grouts is investigated in this paper. The fresh and rheological properties were evaluated by the minislump flow, Marsh cone flow time, Lombardi plate cohesion meter, yield value, and plastic viscosity. The key parameters investigated were the dosages of nanosilica and superplasticizer and temperature of mixing water. Statistical models and isoresponse curves were developed to capture the significant trends. The dosage of nanosilica had a significant effect on the results. The increase in the dosage of nanosilica led to increasing the values of flow time, plate cohesion meter, yield stress, plastic viscosity, heat of hydration at 1 day and 3 days, and compressive strength at 1 day, while reducing the minislump, plastic shrinkage up 24 h, and compressive strength at 3, 7, and 28 days. Conversely, the increase in the dosage of superplasticizer led to decreasing the values of flow time, plate cohesion meter, yield stress, plastic viscosity, heat of hydration at 1 day and 3 days, and compressive strength at 1 day, while increasing the minislump, plastic shrinkage, and compressive strength at 3 and 7 days. Increasing the temperature of mixing water led to a notable increase in the results of minislump, flow time, plastic viscosity, heat of hydration at 3 days, and compressive strength at 1 day, while it reduced the plate cohesion, compressive strength at 3, 7, and 28 days. The statistical models developed in this study can facilitate optimizing the mixture proportions of grouts for target performance by reducing the number of trial batches needed.

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.

Rheological Characteristics of Short Nylon -6 Fiber Reinforced Styrene Butadiene Rubber Containing Epoxy Resin as Bonding Agent

The rheological characteristics of short Nylon-6 fiber-reinforced Styrene Butadiene rubber (SBR) in the presence of epoxy resin-based bonding agent were studied with respect to the effect of shear rate, fiber concentration , and temperature on shear viscosity and die swell using a capillary rheonzeter. All the composites containing bonding agent showed a pseudoplastic nature, which decreased with increasing temperature. Shear viscosity was increased in the presence of fibers. The temperature sensitivity of the SBR matrices was reduced on introduction of fibers. The temperature sensitivity of the melts was found to be lower at higher shear rates. Die swell was reduced in the presence of fibers. Relative viscosity of the composites increased with shear rate. In the presence of epoxy resin bonding agent the temperature sensitivity of the mixes increased. Die swell was larger in the presence of bonding agent.

Studies on the Production, Properties and Processability of Low Protein Latex

Latex protein allergy is a serious problem faced by users of natural rubber latex products. This is severe in health care workers, who are constantly using latex products like examination gloves, surgical gloves etc. Out of the total proteins only a small fraction is extractable and only these proteins cause allergic reactions in sensitized people. Enzymic deproteinisation of latex and leaching and chlorination of latex products are the common methods used to reduce the severity of the problem.Enzyme deproteinisation is a cubersome process involving high cost and process loss.Physical properties of such films are poor. Leaching is a lengthy process and in leached latex products presence of extractable proteins is observed on further storing. Chlorination causes yellowing of latex products and reduction in tensile properties.In this context a more simple process of removal of extractable proteins from latex itself was investigated. This thesis reports the application of poly propylene glycol (PPG) to displace extractable proteins from natural latex. PPG is added to 60 % centrifuged natural latex to the extent of 0.2 % m/rn, subssequently diluted to 30 % dry rubber content and again concentrated to obtain a low protein latex.Dilution of concentrated latex and subsequent concentration lead to a total reduction in non - rubber solids in the concentrate, especially proteins and reduction in the ionic concentration in the aqueous phase of the latex. It has been reported that proteins in natural rubber / latex affect its behaviour in the vulcanisation process. Ionic concentration in the aqueous phase of latex influence the stability, viscosity and flow behaviour of natural latex. Hence, a detailed technological evaluation was carried out on this low protein latex. In this study, low protein latex was compared with single centrifuged latex ( the raw material to almost every latex product), double centrifuged latex ( because dilution and second concentration of latex is accompanied by protein removal to some extent and reduction in the ionic concentration of the aqueous phase of latex.). Studies were conducted on Sulphur cure in conventional and EV systems under conditions of post ~ cure and prevulcanisation of latex. Studies were conducted on radiation cure in latex stage. Extractable protein content in vulcanised low protein latex films are observed to be very low. lt is observed that this low protein latex is some what slower curing than single centrifuged latex, but faster than double centrifuged latex. Modulus of low protein latex films were slightly low. In general physical properties of vulcanised low protein latex films are only siightly lower than single centrifuged latex. Ageing properties of the low protein latex films were satisfactory. Viscosity and flow behaviour of low protein latex is much better than double centrifuged latex and almost comparable to single centrifuged latex. On observing that the physical properties and flow behaviour of low protein latex was satisfactory, it was used for the preparation of examination gloves and the gloves were evaluated. It is observed that the properties are conforming to the Indian Standard Specifications. It is thus observed that PPG treatment of natural latex is a simple process of preparing low protein latex. Extractable protein content in these films are very low.The physical properties of the films are comparable to ordinary centrifuged latex and better than conventionally deprotenized latex films. This latex can be used for the production of examination gloves.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modem polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25-60 degrees C. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60 degrees C), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45-50 degrees C) and had lower strain hardening. Strain hardening measured at 50 degrees C gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of I defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality. (C) 2004 Elsevier B.V. All rights reserved.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modern polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25oC to 60oC. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60oC), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45oC to 50oC) and had lower strain hardening. Strain hardening measured at 50oC gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of 1 defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality.

Rheology of magmas with bimodal crystal size and shape distributions: insights from analog experiments

Magmas in volcanic conduits commonly contain microlites in association with preexisting phenocrysts, as often indicated by volcanic rock textures. In this study, we present two different experiments that inves- tigate the flow behavior of these bidisperse systems. In the first experiments, rotational rheometric methods are used to determine the rheology of monodisperse and polydisperse suspensions consisting of smaller, prolate particles (microlites) and larger, equant particles (phenocrysts) in a bubble‐free Newtonian liquid (silicate melt). Our data show that increasing the relative proportion of prolate microlites to equant pheno- crysts in a magma at constant total particle content can increase the relative viscosity by up to three orders of magnitude. Consequently, the rheological effect of particles in magmas cannot be modeled by assuming a monodisperse population of particles. We propose a new model that uses interpolated parameters based on the relative proportions of small and large particles and produces a considerably improved fit to the data than earlier models. In a second series of experiments we investigate the textures produced by shearing bimodal suspensions in gradually solidifying epoxy resin in a concentric cylinder setup. The resulting textures show the prolate particles are aligned with the flow lines and spherical particles are found in well‐organized strings, with sphere‐depleted shear bands in high‐shear regions. These observations may explain the measured variation in the shear thinning and yield stress behavior with increasing solid fraction and particle aspect ratio. The implications for magma flow are discussed, and rheological results and tex- tural observations are compared with observations on natural samples.

A computational study of some rheological influences on the ""splashing experiment""

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), the extensional viscosity, and the dynamic moduli G` and G ``. In this paper, we shall confine attention to `constant-viscosity` Boger fluids, and, accordingly, we shall limit attention to N(1), eta(E), G` and G ``. We shall concentrate on the ""splashing"" problem (particularly that which arises when a liquid drop falls onto the free surface of the same liquid). Modern numerical techniques are employed to provide the theoretical predictions. We show that high eta(E) can certainly reduce the height of the so-called Worthington jet, thus confirming earlier suggestions, but other rheometrical influences (steady and transient) can also have a role to play and the overall picture may not be as clear as it was once envisaged. We argue that this is due in the main to the fact that splashing is a manifestly unsteady flow. To confirm this proposition, we obtain numerical simulations for the linear Jeffreys model. (C) 2010 Elsevier B.V. All rights reserved.