Abhijit P Deshpande

Microencapsulation is a widely used method for making healing agents used in self-healing composites. In this study, a novel two-stage process was used to make double-walled microcapsules. Dicyclopentadiene–urea formaldehyde (DCPD–UF) microcapsules were synthesized by in situ polymerization of oil-in-water emulsion followed by siloxane coating through ‘sol–gel process’ (DCPD–UF–siloxane microcapsules). Average diameter of microcapsules, UF shell thickness and siloxane coating thickness were found to be 300, 1.4 and 16 µm, respectively. The effect of addition of microcapsules on rheological properties of epoxy was studied. Breaking pattern of single-walled and double-walled microcapsules immersed in epoxy was analyzed by continuous monitoring of the deformation behavior through a rheometer–microscope arrangement, confirming improved mechanical properties of the double-walled microcapsules. In this study, epoxy resin cast specimens with and without microcapsules were prepared and the effect of microcapsules on mechanical properties was examined. Epoxy specimens with double-walled microcapsules were found to be having improved mechanical properties compared to those with single-walled microcapsules. Finally, healing efficiency of DCPD–UF–siloxane microcapsules in epoxy was observed to be marginally higher, and therefore, this double-walled microcapsule system is shown to be a promising candidate for further self-healing composite investigations.

Curdlan, a polysaccharide known to be used in the food packaging industry that gels out when exposed to higher temperatures, leading to different kinds of gel structures. The triple-helical structural formations of the curdlan gels are studied in the present work with varying concentrations and heating rate. The gel strength and associativeness of the molecules are analysed using rheology as a tool. The gelation behaviour of various curdlan gels that were derived from different species could be distinguished using the modified Hill equation parameters.

Rheological behavior of asphalt is strongly affected by loading conditions, temperature and environment. One of the main challenges in understanding the rheology of asphalt is to relate the chemical constituents and the micro-structure of asphalt on one hand to its rheological behavior on the other hand. In this work, nonlinear rheological behaviour of asphalt was investigated using a structural rheological model. A first order kinetic equation to describe structural changes in asphalt has been incorporated with the nonlinear rheological model of White-Metzner. The resulting set of governing equations was solved numerically to describe the rheology of asphalts. Different modes of rheological testing and asphalts with different compositions were considered. An analysis and comparison of model behaviour with experimental data from the literature is carried out in both stress growth at constant shear rate and oscillatory shear modes. A strategy is proposed for the estimation and tuning of the model parameters based on available experimental data and literature. Qualitatively, the model can capture the rheological behaviour of non-Newtonian fluids such as asphalt under different modes of rheological testing. Quantitative analysis from this work shows that the model describes the rheological behaviour of asphalt for the temperature range of 20-60°C. It is demonstrated that a single set of equations tuned with the steady shear experimental data can be used to predict the nonlinear rheological behaviour of asphalts. In addition, it is shown that the model parameters can be related to the chemical composition of asphalts. © Appl. Rheol.

Gelation of crosslinking polymers, with ionic groups, is of interest in membrane processing of these materials. The gelation of polyvinyl alcohol in the presence of an ionic crosslinker, sulfosuccinic acid, was monitored through rheological measurements. The evolution of rheological material functions during film formation, which involves solvent evaporation and crosslinking, was observed at different polymer and crosslinker concentrations. Relative effect of water evaporation leading to physical gelation and the chemical crosslinking was examined. To understand the effect of crosslinker type, the rheology of nonionic crosslinker, glutaraldehyde was also examined. The gel points as well as network parameters for these covalent networking systems were different and depended on crosslinker type and polymer/crosslinker concentrations. However, qualitative evolution of rheological behavior during film formation was largely similar, demonstrating the dominating effect of solvent evaporation. Crosslinking in the absence of solvent evaporation was examined at different temperatures. It can be concluded that similar mechanism was involved, independent of temperature, in the temperature range of interest. The effect of crosslinker concentration on evolution of rheological properties near gelation was insignificant for ionic crosslinker though marginally significant for nonionic crosslinker. © 2010 Springer-Verlag.

There is an increasing demand for designing controlled drug delivery systems with materials which are more biocompatible, economical and materials which can be processed easily. Poly (vinyl alcohol) (PVA) and hyaluronic acid (HA) are promising polymers for applications in drug delivery. PVA forms gel based on the acetal bridges when crosslinked with glutaraldehyde (GA). On the other hand, HA a natural polymer, forms gel with divinyl sulfone (DVS) as a crosslinker. PVA and HA blends upon crosslinking PVA with GA or HA with DVS, in the presence of the other polymer, form gels that are more adaptable to the drug delivery systems. In this work, the mechanical properties and swelling behaviour of PVAHA gels were characterized. The effect of composition on viscoelastic moduli and degree of swelling was determined. The storage modulus (G") of various gels made of PVA, HA and PVAHA blends were measured using rheology and compared with the values available in the literature. Swelling properties were measured and compared among various PVA and HA gels. Collagen is added to PVA solution and the rheological properties were measured in the gel state. Based on the values of storage modulus, gels of various compositions of PVA, HA and collagen might be selected as potential biomaterials for drug delivery system depending on careful understanding the type of application. © 2014, DESIDOC.

Standard laboratory ageing methods of bitumen only take into account the effect of thermo-oxidation during the service life of a pavement but the effect of high energy cosmic radiation on site is not simulated in these procedures. The aim of the present work is to compare the laboratory simulated short term bitumen ageing (rolling thin film oven test) with ageing produced by short exposures of bitumen samples to Ultra Violet and gamma radiation. The influence of ageing agents on the thermal properties and rheological performance of the pristine and modified bitumen binders has been evaluated in this study. The thermal behavior of various aged bitumens is characterized by both isothermal as well as non-isothermal thermogravimetric analysis. The thermoanalytic investigations on bituminous samples are carried out to evaluate the thermal stabilities and activation energies of the binders and the life time prediction of the materials is made with the help of the kinetic information. It is found that modified bituminous binders are more resistant to heat and radiation. Different rheological tests are conducted by dynamic shear rheometer to examine the effect of ageing in terms of bitumen oxidation and polymer phase degradation which has a major consequence on high temperature rutting or low temperature cracking. Type of modifier is found to be of decisive importance. Creep and recovery tests show that the structure-time dependency of pristine aged bitumen is influenced much by stress and temperature than in the case of modified aged bitumens. The study has revealed that the elastomeric modifier protects the bituminous binder more than plastic modifier or nano filler. Finally, a fair correlation has been made between standard RTFO ageing and radiation aging. © 2012 RILEM.