A comparative analysis of moisture transport models as applied to an epoxy binder

The results of experimental and theoretical investigations into the kinetics of moisture sorption by a neat epoxy resin obtained from RAE Industries (Reapox 520, D523) are reported. The sorption process was realized in atmospheres with a constant relative humidity of 33, 53, 75, 84, and 97% and a temperature of 50°C. The results obtained showed that the diffusion behavior of epoxy resin did not obey Fick’s law under the experimental conditions considered. Consequently, the application of a non-Fickian diffusion model was necessary. For this purpose, two-phase moisture sorption models, a model with a time-dependent diffusivity, a two-phase material model, as well as relaxation and convection models of anomalous diffusion, were considered. The model parameters were obtained from the approximation of experimental sorption data. A comparative analysis of the sorption models was performed, and the specific features of their applications were estimated. The two-phase material model and the model with varying diffusivity were found to be the most suitable ones due to a good agreement between calculation results and experimental data and the rather small (three or four) number of parameters, which make them more flexible and physically more justified than the classical Fick’s model with its two parameters. __________ Translated from Mekhanika Kompozitnykh Materialov, Vol. 43, No. 4, pp. 555–570, July–August, 2007.     

Mössbauer investigation of magnetite nanoparticles incorporated in a mesoporous polymeric template

Mössbauer spectroscopy was used in this study to investigate magnetite-based nanocomposites, using mesoporous styrene-divinylbenzene (Sty-DVB) microspheres as the hosting template. The magnetite content was increased in the polymeric template by performing several in situ chemical reactions (one to six cycles) in the hosting material. We found the Mössbauer linewidth associated to site-A increasing with the relative increase of iron in site-A. The Mössbauer linewidth associated to site-B decreases with the relative decrease of iron in site-B. We explain our findings by assuming local change in the homogeneity associated to changes in the relative iron population in sites A and B.     

I-STMAS,a new high-resolution solid-state NMR method for half-integer quadrupolar nuclei

In complement to the previously proposed multiple-quantum magic-angle-spinning (MQMAS) and satellite transition MAS (STMAS) sequences, we describe a new two-dimensional high-resolution method, inverse-STMAS (I-STMAS) that allows second-order quadrupolar averaging. Like STMAS, I-STMAS correlates second-order quadrupole dephasing occurring on coherences related to the central transition (CT) and satellite transitions (STs), but does it in a reverse manner: CT evolves during the t₁ period while STs are detected during t₂. Although STMAS and I-STMAS are symmetric, there are some interesting and useful differences between the two methods. For example, we show that during the acquisition time t₂, it is possible to over-sample the data and then to process them to suppress the CT–CT correlation resonance.     

NMR heteronuclear correlation between quadrupolar nuclei in solids

We show for the first time that it is possible to acquire high-resolution heteronuclear NMR correlation experiments in solid state between second-order-broadened half integer quadrupolar nuclei (i.e., 27Al and 17O) using the scalar J-coupling. The sensitivity of the experiment is dramatically improved at high fields (gain proportional to the fourth power of the principal field) with a combination of signal enhancement techniques. This turns a challenging experiment into a real tool. We apply this experiment to characterize a calcium aluminate glass in which we prove the presence of tricluster mu3 oxygen sites and describe the signature of their directly bonded aluminum sites. Applications involve a large range of possible pairs of quadrupolar nuclei in different materials, such as glasses, porous or mesoporous framework materials, zeolites, hybrid organic-inorganic, and bioinvolved materials.     

High-resolution heteronuclear correlation spectra between 31P and 27Al in microporous aluminophosphates

A solid-state nuclear magnetic resonance (NMR) experiment, which provides high-resolution two-dimensional heteronuclear correlation (HETCOR) spectra between 27Al and 31P, is described. The first part of the experiment uses triple-quantum or quintuple-quantum magic-angle spinning (MQMAS) NMR of spin-5/2 nuclei (27Al) to produce an isotropic echo that is unaffected by the second-order quadrupolar broadening. The magnetization is then transferred to the spin-1/2 (31P) nuclei via cross-polarization (CP), resulting in isotropic resolution in both spectral dimensions. To illustrate its usefulness, this method (referred to as MQHETCOR) is applied to two important microporous framework aluminophosphates, hydrated VPI-5 and AIPO4-40.     

Paradigms and paradoxes: the aromaticity of 6:6 fused carbocycles and heterocycles as an extension of a study of indane and indene derivatives

Aromaticity is of continuing interest to the organic chemical community. We recently presented a model for the aromaticity of carbocyclic and heterocyclic derivatives of indane and indene, i.e. species defined as benzenes fused to 5-membered rings. The current note extends this model to related derivatives of tetralin and naphthalene, benzenes fused to 6-membered rings. Explicit species discussed herein are: benzopyran, both α- and β-tetralone, coumarin and quinoline.     

Antinociceptive and anti-inflammatory effects of a lectin-like substance from Clitoria fairchildiana R. Howard seeds

Lectins are proteins that have the ability to bind specifically and reversibly to carbohydrates and glycoconjugates, without altering the structure of the glycosyl ligand. They are found in organisms such as viruses, plants and humans, and they have been shown to possess important biological activities. The objective of this study was to purify and characterize lectins in the seeds of Clitoria fairchildiana, as well as to verify their biological activities. The results indicated the presence of a lectin (CFAL) in the glutelin acid protein fraction, which agglutinated native rabbit erythrocytes. CFAL was purified by column chromatography ion-exchange, DEAE-Sephacel, which was obtained from a peak of protein retained in the matrix by applying 0.5 M NaCl using the step-wise method. Electrophoretic analysis of this lectin in SDS-PAGE indicated a two band pattern protein molecular mass of approximately 100 and 116 kDa. CFAL proved to be unspecific to all carbohydrates/glycoconjugates in common use for the sugar inhibition test. This lectin showed no significant cytotoxicity to human red blood cells. It was observed that CFAL has anti-inflammatory activity in the paw edema induced by carrageenan model, in which a 64% diminution in edema was observed. Antinociceptive effects were observed for CFAL in the abdominal writhing test (induced by acetic acid), in which increasing doses of the lectin caused reduction in the number of contortions by up to 72%. It was concluded that the purified and characterized lectin from the seeds of Clitoria fairchildiana has anti-inflammatory and antinociceptive activity, and is not cytotoxic to human erythrocytes.     

Energetics of naphthalene derivatives,IV+: a calorimetric and calculational thermochemical study of the isomeric naphthalenemethanols

The standard (p°?=?0.1?MPa) molar energies of combustion in oxygen, at T?=?298.15?K, of 1-naphthalenemethanol and 2-naphthalenemethanol were measured by static bomb calorimetry. The values of the standard molar enthalpies of sublimation, at T?=?298.15?K, were obtained by Calvet microcalorimetry. Combining these results the standard molar enthalpies of formation of the compounds, in the gas phase, at T?=?298.15?K, have been calculated.

Energetics of naphthalene derivatives, IV+ ⁺Paper III: Roux, M.V., Temprado, M., Notario, R., Verevkin, S.P., Emel’yanenko, V.N., DeMasters, D.E., Liebman, J.F. Mol. Phys., 102, 1909 (2004). : a calorimetric and calculational thermochemical study of the isomeric naphthalenemethanols

All authors

M. A. R. Matos, V. M. F. Morais, C. C. S. Sousa, M. V. Roux, R. Notario &; J. F. Liebman

https://doi.org/10.1080/00268970701413891

Published online:

04 December 2010

Table     

Direct Evaluation of Cohesive Law in Mode I of Pinus pinaster by Digital Image Correlation

The direct identification of the cohesive law in pure mode I of Pinus pinaster is addressed in this work. The approach couples the double cantilever beam (DCB) test with digital image correlation (DIC). Wooden beam specimens loaded in the radial-longitudinal (RL) fracture propagation system are used. The strain energy release rate in mode I (G _I) is uniquely determined from the load–displacement curve by means of the compliance-based beam method (CBBM). This method relies on the concept of equivalent elastic crack length (a _eq) and therefore does not require the monitoring of crack propagation during test. DIC measurements are processed with two different purposes. Firstly, the physical evidence of a _eq is discussed with regard to actual estimation of the crack length based on post-processing full-field displacement measurements. Secondly, the crack tip opening displacement in mode I (w _I) is determined from the displacements near the initial crack tip. The cohesive law in mode I (σ _I???w _I) is then identified by numerical differentiation of the G _I???w _I relationship. The methodology and accuracy on this reconstruction are addressed. Moreover, the proposed procedure is validated by finite element analyses including cohesive zone modelling. It is concluded that the proposed data reduction scheme is adequate for assessing the cohesive law in pure mode I of P. pinaster.