Rheological and mechanical properties of hydroxypropyl methylcellulose-based hydrogels and cryogels controlled by AOT and SDS micelles.

HYPOTHESIS: The type and concentration of surfactants affect the rheological behavior of hydroxypropyl methylcellulose (HPMC) chains in hydrogels, influencing the microstructure and mechanical properties of HPMC cryogels. EXPERIMENTS: Hydrogels and cryogels containing HPMC, AOT (bis (2-ethylhexyl) sodium sulfosuccinate or dioctyl sulfosuccinate salt sodium, two C8 chains and sulfosuccinate head group), SDS (sodium dodecyl sulfate, one C12 chain and sulfate head group), and sodium sulfate (salt, no hydrophobic chain) at different concentrations were investigated using small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), rheological measurements, and compressive tests. FINDINGS: SDS micelles bound to the HPMC chains building "bead necklaces", increasing considerably the storage modulus G' values of the hydrogels and the compressive modulus E values of the corresponding cryogels. The dangling SDS micelles promoted multiple junction points among the HPMC chains. AOT micelles and HPMC chains did not form "bead necklaces". Although AOT increased the G' values of the hydrogels, the resulting cryogels were softer than pure HPMC cryogels. The AOT micelles are probably embedded between HPMC chains. The AOT short double chains rendered softness and low friction to the cryogel cell walls. Therefore, this work demonstrated that the structure of the surfactant tail can tune the rheological behavior of HPMC hydrogels and hence the microstructure of the resulting cryogels.

Tuning the Mechanical and Thermal Properties of Hydroxypropyl Methylcellulose Cryogels with the Aid of Surfactants.

The mechanical and thermal properties of cryogels depend on their microstructure. In this study, the microstructure of hydroxypropyl methylcellulose (HPMC) cryogels was modified by the addition of ionic (bis (2-ethylhexyl) sodium sulfosuccinate, AOT) and non-ionic (Kolliphor® EL) surfactants to the precursor hydrogels (30 g/L). The surfactant concentrations varied from 0.2 mmol/L to 3.0 mmol/L. All of the hydrogels presented viscous behavior (G″ > G'). Hydrogels containing AOT (c > 2.0 mmol/L) led to cryogels with the lowest compressive modulus (13 ± 1 kPa), the highest specific surface area (2.31 m2/g), the lowest thermal conductivity (0.030 W/(m·°C)), and less hygroscopic walls. The addition of Kolliphor® EL to the hydrogels yielded the stiffest cryogels (320 ± 32 kPa) with the lowest specific surface area (1.11 m2/g) and the highest thermal conductivity (0.055 W/(m·°C)). Density functional theory (DFT) calculations indicated an interaction energy of -31.8 kcal/mol due to the interaction between the AOT sulfonate group and the HPMC hydroxyl group and the hydrogen bond between the AOT carbonyl group and the HPMC hydroxyl group. The interaction energy between the HPMC hydroxyl group and the Kolliphor® EL hydroxyl group was calculated as -7.91 kcal/mol. A model was proposed to describe the effects of AOT or Kolliphor® EL on the microstructures and the mechanical/thermal properties of HPMC cryogels.

Dating human occupation at Toca do Serrote das Moendas, São Raimundo Nonato, Piauí-Brasil by electron spin resonance and optically stimulated luminescence.

Excavation of Toca do Serrote das Moendas, in Piauí state, Brazil revealed a great quantity of fossil wild fauna associated with human remains. In particular, fossils of a cervid (Blastocerus dichotomus) were found, an animal frequently pictured in ancient rock wall paintings. In a well-defined stratum, two loose teeth of this species were found in close proximity to human bones. The teeth were independently dated by electron spin resonance (ESR) in two laboratories. The ages obtained for the teeth were 29 ± 3 ka (thousands of years) and 24 ± 1 ka. The concretion layer capping this stratum was dated by optically stimulated luminescence (OSL) of the quartz grains to 21 ± 3 ka. As these values were derived independently in three different laboratories, using different methods and equipment, these results are compelling evidence of early habitation in this area.

TL, OSL and C-14 dating results of the sediments and bricks from mummified nuns' grave.

This paper presents the results of TL and OSL dating of soil and fragments of bricks from a grave, which was occupied by two mummified nuns, found at "Luz" Monastery, located in the state of São Paulo, Brazil. The TL and OSL ages were compared to C-14 dating ones obtained from bone collagens of the mummies. The majority of the ages is related to the eighteenth century. The gamma-ray spectroscopy was used to evaluate natural radioisotope concentrations in the samples, and by using these concentrations the annual dose rates, from 3.0 to 5.3 Gy/kyr, were obtained. Neutron activation analysis was performed and the radioisotope contents results are in agreement with those obtained by gamma-ray spectroscopy. The contents of U, Th and Ce elements were higher than those found in usual sediments.

Luminescence dating of quaternary deposits in geology in Brazil.

In the present work, systematic dating by luminescence methods has been done on 50 Quaternary geological samples within the study area of São Paulo State, Brazil. Bleaching experiments showed that residual TL intensity of 375 degrees C peak, of the quartz, was obtained after 10 h of sunlight exposition. Intensities decays of the 325 and 375 degrees C TL peaks can be fitted using second order exponential equation. Paleodose values were evaluated using regeneration methods with multiple aliquots. Samples dated indicate preliminary ages varying from 9 +/- 1 to 935 +/- 130 ka for colluvio-elluvial deposits, and from 17 +/- 2 to 215 +/- 30 ka for alluvial deposits of the study area. They cover four peneplained surfaces shaped during the Quaternary: I (1000-400 ka), II (400-120 ka), III (120-10 ka) and IV (10 ka until today), in decreasing order.