Applying reactive models to column experiments to assess the hydrogeochemistry of seawater intrusion: optimising ACUAINTRUSION and selecting cation exchange coefficients with PHREEQC

Three sets of laboratory column experimental results concerning the hydrogeochemistry of seawater intrusion have been modelled using two codes: ACUAINTRUSION (Chemical Engineering Department, University of Alicante) and PHREEQC (U.S.G.S.). These reactive models utilise the hydrodynamic parameters determined using the ACUAINTRUSION TRANSPORT software and fit the chloride breakthrough curves perfectly. The ACUAINTRUSION code was improved, and the instabilities were studied relative to the discretisation. The relative square errors were obtained using different combinations of the spatial and temporal steps: the global error for the total experimental data and the partial error for each element. Good simulations for the three experiments were obtained using the ACUAINTRUSION software with slight variations in the selectivity coefficients for both sediments determined in batch experiments with fresh water. The cation exchange parameters included in ACUAINTRUSION are those reported by the Gapon convention with modified exponents for the Ca/Mg exchange. PHREEQC simulations performed using the Gains-Thomas convention were unsatisfactory, with the exchange coefficients from the database of PHREEQC (or range), but those determined with fresh water – natural sediment allowed only an approximation to be obtained. For the treated sediment, the adjusted exchange coefficients were determined to improve the simulation and are vastly different from those from the database of PHREEQC or batch experiment values; however, these values fall in an order similar to the others determined under dynamic conditions. Different cation concentrations were simulated using two different software packages; this disparity could be attributed to the defined selectivity coefficients that affect the gypsum equilibrium. Consequently, different calculated sulphate concentrations are obtained using each type of software; a smaller mismatch was predicted using ACUAINTRUSION. In general, the presented simulations by ACUAINTRUSION and PHREEQC produced similar results, making predictions consistent with the experimental data. However, the simulated results are not identical to the experimental data; sulphate (total S) is overpredicted by both models, most likely due to such factors as the kinetics of gypsum, the possible variations in the exchange coefficients due to salinity and the neglect of other processes.

Ethylene vinyl acetate/nanoclay-based pigment composites: Morphology, rheology, and mechanical, thermal, and colorimetric properties

In this study, a new type of nanopigment, obtained from a nanoclay (NC) and a dye, was synthesized in the laboratory, and these nanopigments were used to color an ethylene vinyl acetate (EVA) copolymer. Several of these nanoclay-based pigments (NCPs) were obtained through variations in the cation exchange capacity (CEC) percentage of the NC exchanged with the dye and also including an ammonium salt. Composites of EVA and different amounts of the as-synthesized nanopigments were prepared in a melt-intercalation process. Then, the morphological, mechanical, thermal, rheological, and colorimetric properties of the samples were assessed. The EVA/NCP composites developed much better color properties than the samples containing only the dye, especially when both the dye and the ammonium salt were exchanged with NC. Their other properties were similar to those of more conventional EVA/NC composites.

Linear low-density polyethylene colored with a nanoclay-based pigment: Morphology and mechanical, thermal, and colorimetric properties

In this study, a novel kind of hybrid pigment based on nanoclays and dyes was synthesized and characterized. These nanoclay-based pigments (NCPs) were prepared at the laboratory with sodium montmorillonite nanoclay (NC) and methylene blue (MB). The cation-exchange capacity of NC exchanged with MB was varied to obtain a wide color gamut. The synthesized nanopigments were thoroughly characterized. The NCPs were melt-mixed with linear low-density polyethylene (PE) with an internal mixer. Furthermore, samples with conventional colorants were prepared in the same way. Then, the properties (mechanical, thermal, and colorimetric) of the mixtures were assessed. The PE–NCP samples developed better color properties than those containing conventional colorants and used as references, and their other properties were maintained or improved, even at lower contents of dye compared to that with the conventional colorants.

Effect of the intercalated cation-exchanged on the properties of nanocomposites prepared by 2-aminobenzene sulfonic acid with aniline and montmorillonite

Polymer/montmorillonite nanocomposites were prepared. Intercalation of 2-aminobenzene sulfonic acid with aniline monomers into montmorillonite modified by cation was followed by subsequent oxidative polymerization of monomers in the interlayer spacing. The clay was prepared by cation exchange process between sodium cation in (M–Na) and copper cation (M–Cu). XRD analyses show the manifestation of a basal spacing (d-spacing) for M–Cu changes depending on the inorganic cation and the polymer intercalated in the M–Cu structure. TGA analyses reveal that polymer/M–Cu composites is less stable than M–Cu. The conductivity of the composites is found to be 103 times higher than that for M–Cu. The microscopic examinations including TEM picture of the nanocomposite demonstrated an entirely different and more compatible morphology. Remarkable differences in the properties of the polymers have also been observed by UV–Vis and FTIR, suggesting that the polymer produced with presence of aniline has a higher degree of branching. The electrochemical behavior of the polymers extracted from the nanocomposites has been studied by cyclic voltammetry which indicates the electroactive effect of nanocomposite gradually increased with aniline in the polymer chain.

The influence of surfactant loading level in a montmorillonite on the thermal, mechanical and rheological properties of EVA nanocomposites

In this work, montmorillonite (Mt) has been organically modified with ethyl hexadecyl dimethyl ammonium (EHDDMA) in 20, 50, 80 and 100% of the nominal exchange capacity (CEC) of the Mt. A full characterization of the organo-montmorillonite (OMt) obtained has been made, including thermal analysis, X-Ray Diffraction, elemental analysis CHN and nitrogen adsorption. According to the results, 12% in mass of the surfactant added is strongly retained by the Mt. When the mass percentage of EHDDMA exchanged in the OMt is increased up to this level, the interactions OMt–EHDDMA are steeply reduced depending on the EHDDMA content. Clay polymer nanocomposites (CPN) were prepared by melt mixing of EVA and different loads of OMt. The CPN were compress molded to obtain 1 mm thick sheets, which have been characterized according to their mechanical, thermal and rheological behaviors. The major changes in the structure of the OMt are obtained for low contents of EHDDMA. Nevertheless, the CPN containing OMt exchanged at 20 and 50% of the CEC show relatively low effect of the EHDDMA while the mechanical response and rheological behavior of CPN with OMt modified at 80 and 100% of the CEC are much more pronounced.

Characterisation of montmorillonites simultaneously modified with an organic dye and an ammonium salt at different dye/salt ratios. Properties of these modified montmorillonites EVA nanocomposites

In this work, a sodium montmorillonite (Na+-Mt) was modified with two molecules simultaneously, an organic dye, methylene blue (MB), and ethyl hexadecyl dimethyl ammonium (EHDDMA). The synthesised organo-montmorillonites (OMt) combining different proportions of the two molecules were thoroughly characterised and mixed with ethylene vinyl acetate copolymer (EVA) in order to check the ability of these OMt as pigments and reinforcing additives. The synthesised OMt combining both surfactants, MB and EHDDMA, present higher interlayer distances than those with only MB, which were employed in previous works as nanopigments. When these OMt were incorporated in the EVA matrix, the obtained clay polymer nanocomposites (CPN) showed a high exfoliation degree of the OMt in the polymer, in such a way that at 80% of the cationic exchange capacity (CEC) of the Mt exchanged with EHDDMA, most of the OMt was exfoliated. Moreover, all the obtained CPN showed an increase in the Young's Moduli compared to the EVA reference, and especially those containing higher amounts of MB. The thermal stability of the CPN also increases with the MB content, compared to other CPN including conventional surfactants. The hiding power and colouring power achieved in the CPN are higher even with a much lower load of MB when EHDDMA is exchanged in the Mt.