Mineralogy of agricultural soil of selected regions of South Western Karnataka, Peninsular India.

Agricultural soils of selected regions of Southwestern Karnataka, Peninsular India, were subjected to systematic mineralogical characterization along with the study of soil physical properties. Physical properties such as soil texture and micro porosity were studied using particle size analyses and positron annihilation lifetime analysis (PALS) technique, respectively. The latter was used to analyze micro porosity of agricultural soil. Both major and minor minerals were identified and confirmed by some analytical techniques like thin section study, powder X-ray diffraction, X-ray fluorescence spectroscopy and Fourier transform infrared spectroscopy.

Influence of polar groups in binary polymer blends on positronium formation.

The present work studied the role of the polar group unconjugated oxygen on the inhibition of positronium (Ps) formation in two binary blends made from a set of chosen constituent polymers with polar and weakly polar groups (nonpolar). The polymer blend samples of PVC-EVA and PVC-SAN were investigated by coincidence Doppler broadening and positron lifetime techniques. The strong polar acetate group in the EVA contributed to positron annihilation with electrons of unconjugated oxygen (-C(+)=O(-)) as revealed by the momentum distribution curves peaking around 17 P(L) (10(-3) m(0)c). The ortho-Ps intensity indicated the unconjugated oxygen shows about a 28% Ps reduction even in the presence of a strong Ps inhibiting halogen (Cl(-)). In contrast, this effect was not seen in the PVC-SAN blends since SAN contains a weakly polar (nonpolar) acrylonitrile group (C≡N). Our results indicate the chlorine of PVC in the blends is a major contributor to Ps inhibition through the formation of a (Cl(-)-e(+)) bound state but the unconjugated oxygen in EVA of the PVC-EVA blend also plays a similar, but lesser, role.

Chemical and photochemical degradation of human hair: a free-volume microprobe study.

The microstructural changes in human hair due to chemical and photochemical oxidative processes have been monitored in terms of free volume employing Positron Annihilation Lifetime Spectroscopy (PALS). The results show that upon UV exposure the photosensitive amino acid residues present in the amorphous domains of virgin/bleached hair cross-link under ambient conditions. Further, the bleached hair readily undergoes photodamage in comparison with the virgin hair implying the diminished photoprotective action of the melanin granules within it. Swelling of hair fiber was evident in the early stages of UV exposure (<300h), bleaching, and humidification subsequent to irradiation. Swelling and cross-linking were the two main processes observed following UV exposure, which oppositely affect the free volume holes size. Supplementary techniques such as DSC and XRD were used to support/extend the interpretation of the PALS results. The UV irradiation resulted in reduction of the average crystallite size in hair, which is attributed to the possible fragmentation of protein domains. The present work is the first positron lifetime measurement on human hair that demonstrates the ability of PALS to provide information on hair damage at molecular level, a vital input for cosmetic industry and applicable to biopolymers research as well.

Diffusion of permanent liquid dye molecules in human hair investigated by positron lifetime spectroscopy.

The diffusion behavior of a commercial permanent liquid hair dye in human hair has been investigated using positron annihilation lifetime spectroscopy (PALS) and gravimetric sorption method. The positron technique makes it possible to non-invasively characterize the angstrom sized free volume holes in hair, which are supposed to be express pathways for diffusion of small molecules. The o-Ps lifetime parameters tau3 and I3 decrease rapidly during the first 60 min of sorption time. The overall decrease in o-Ps lifetime (tau3) was well over 200 ps and o-Ps intensity (I3) drops by 3.5%. These positron results are explained in terms of dye molecules filling the free volume holes and hair morphology. The dye penetrates the cuticle rapidly, but slowly in cortex. The first hour of dyeing appears to be the most effective period of deposition of dye molecules within hair. These results are well corroborated by the sorption results which suggest that the dye diffusion is essentially a diffusion controlled (i.e. Fickian) process, with no observable relaxation effects. In the latter part of the sorption, where positron parameters remain almost constant, mass increase might be due to surface adhesion. These two stages of sorption are well separated by the positron technique. The sorption curve also yielded an average value of apparent diffusivity of the dye in hair. From this study, we conclude that the free volume theory and positron technique, widely used in polymer research, may expediently be used to understand hair properties, more importantly diffusion of dye molecules.

Influence of spoliation in poly(2-hydroxy ethyl methacrylate) soft contact lens on its free volume and optical transparency.

The calcification in poly(2-hydroxy ethyl methacrylate) contact lens was investigated using positron annihilation spectroscopy (PLS). The two poly(2-hydroxy ethyl methacrylate) (PHEMA) lenses of different companies were calcified employing a simple mechanism of calcification in abiotic aqueous solutions. The calcium deposit was analyzed using energy dispersive X-ray spectroscopy (EDS). Calcified lenses showed decrease in ortho-positronium (o-Ps) lifetime and free volume hole size of the lens material suggesting diffusion of Ca2+ into these cavities. The change in optical property viz. refractive index of these calcified lenses were measured and correlated with positron results. To find a better correlation, a series of worn spoilt PHEMA lenses of the same power with mainly calcium deposits, were similarly characterized using PLS and refractive index. These results correlate well with the free volume of the material. For hydrophilic lenses this correlation is reported for the first time.

Glucose and water diffusion kinetics study in a fluorosilicone acrylate contact lens material by positron lifetime spectroscopy.

A comparative study of water and glucose sorption in a rigid gas-permeable contact lens polymer, Fluoroperm 92, has been carried out using positron annihilation lifetime spectroscopy, gravimetric analysis and refractive index measurements. The water sorption in FP92 is non-Fickian, whereas for glucose sorption it changes to Fickian. Glucose molecules reduce the interaction of water molecules with the polymer, resulting in more free water than bound water. It is observed that lenses which contain more bulk-water are prone to lens dehydration and corneal desiccation. The present results indicate that, in case of diabetics, as the glucose level increases in the aqueous humor, there would be more free water than bound water, which increases the propensity for corneal desiccation. The change in refractive index with increase in glucose content indicates decrease in optical transparency of the material.

Free volume study on calcification process in an intraocular lens after cataract surgery.

An opacified intraocular lens explanted from a patient in the postoperative period after phacoemulsification was investigated to find the cause of opacification. From the UV-visible and energy dispersive X-ray spectroscopy (EDS) measurements, the opacification in the present case seems to be due to calcification of the intraocular lens and not due to modification in the UV absorber material of the lens. The average free volume size of the intraocular lens both in unimplanted and explanted state were obtained from positron lifetime spectroscopy (PLS). Further, the combined FTIR and PLS results indicate that calcium gets into the free volume cavities of the intraocular lens matrix as a cationic moiety, may be in the form of Ca(++). The small decrease in glass transition temperature of the calcified lens seems to indicate the plasticizing action of calcium ions. The present results could be of some use in the design of the intraocular lens material in which calcification would be minimum.

A free volume microprobe study of water sorption in a contact lens polymer.

The kinetics of moisture uptake in a rigid gas-permeable contact lens material, Fluoroperm60, has been investigated. The free volume changes accompanied by the sorption of water were monitored using the positron lifetime spectroscopy (PLS) technique. The positron results indicated swelling in the initial stages of sorption and the filling of vacant free volume sites with water in the later stages of sorption. The sorption curve suggests that the diffusion process in this polymer follows the dual-mode sorption model. Using this model, it was possible to separate Fickian-controlled diffusion and relaxation-controlled diffusion. Furthermore, the positron results combined with the sorption results indicated that Fujita's free volume theory does not seem to be valid for the diffusion process in the present sample under study. The variation of the permeability as a function of the free volume suggests that the amount of water in a contact lens is a measure of its permeability.