Modeling of flow‐induced crystallization in blends of isotactic polypropylene and poly(ethylene‐co‐octene)

Poly(ethylene‐co‐octene) (PEOc) has been shown to provide a high toughening contribution to isotactic polypropylene (iPP). The theoretical modeling of flow‐induced crystallization (FIC) of blends of iPP and PEOc is not much reported in the literature. The aim of the present work is to clarify the FIC of iPP upon addition of PEOc in terms of theoretical modeling. The crystallization of iPP and PEOc blends in flow is simulated by a modified FIC model based on the conformation tensor theory. Two kinds of flow fields, shear flow and elongational flow, are considered in the prediction to analyze the influence of flow field on the crystallization kinetics of the polymer. The simulation results show that the elongation flow is much more effective than shear flow in reducing the dimensionless induction time of polymer crystallization. In addition, the induction time of crystallization in the blends is sensitive to the change of shear rate. In comparison with experimental data, the modified model shows its validity for the prediction of the induction time of crystallization of iPP in the blends. Moreover, the simulated relaxation time for the blends becomes longer with increasing percentage of PEOc in the blends. Copyright © 2012 Society of Chemical Industry     

Influence of moisture content on the specific methanogenic activity of dry mesophilic municipal solid waste digestate

The objective of this study was to evaluate the influence of moisture content on the specific methanogenic activity (SMA) of a fresh dry mesophilic digestate from a municipal solid waste digester plant. For this purpose, SMA tests were performed under mesophilic conditions in 500 mL glass bottles of volume used as batch reactors, during a period of 20–25 days. Cellulose, propionate and acetate were used as substrates (5 g_COD kg^?1 digestate) at four different moisture contents, ranging from 65 to 82%. The moisture content strongly influenced the specific methanogenic activity. The highest SMA values were observed at a moisture content of 82% (11.1, 7.8 and 6.0 mg_COD g_VS^?1 d^?1 for cellulose, propionate and acetate spikes, respectively). SMA and moisture content were found to be linearly linked. Dry digestion at low water content is thus detrimental to the biological activity, probably due to physical limitations. Copyright © 2011 Society of Chemical Industry     

Kinetics of adsorption of sulfur mustard on Al2O3 nanoparticles with and without impregnants

BACKGROUND: Chemical warfare (CW) agents are highly toxic compounds and have been used in war to produce physical immobilization, so safe and effective ways to detoxify them without endangering human life or the environment is of great concern. One of the important ways to achieve protection against CW agents contaminating air is to utilize suitable adsorbent materials, e.g. activated carbon, nanoparticles, etc. In the present study nanoparticles, synthesized through sol–gel processes and loaded with reactive compounds have been used for the degradation of CW agents and to understand their adsorption kinetics using Fickian and linear driving force models. RESULTS: Nanoparticles of AP‐Al₂O₃ (aerogel‐produced alumina) in the size range 2–30 nm with high surface area (375 m² g^?1) were produced by an alkoxide‐based synthesis, and then characterized using N₂‐Brunauer–Emmet–Teller (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. Thereafter, these were impregnated, and finally tested for kinetics of adsorption of sulfur mustard (HD) under static conditions. The kinetics was studied using linear driving force and Fickian diffusion models and the kinetics parameters determined. CONCLUSION: AP‐Al₂O₃ with 10% impregnation of 9‐molybdo‐3‐vanadophosphoric acid (10%, w/w) showed the maximum uptake (640 mg g^?1) of HD. The highest adsorption potential indicated that the adsorption was due not only to physisorption but also involved chemisorption. Values of the diffusional exponent indicated the mechanism to be Fickian and anomalous. Hydrolysis, dehydrochlorination and oxidation reactions (identified using gas chromatography‐mass spectrometry (GC/MS)) were found to be the route of degradation of HD over the prepared nanoparticle based adsorbents. Copyright © 2009 Society of Chemical Industry     

Optimization of kinetic data for two‐stage batch adsorption of Pb(II) ions onto tripolyphosphate‐modified kaolinite clay

BACKGROUND: Most adsorption studies consider only the adsorption of pollutants onto low cost adsorbents without considering how equilibrium and kinetic data can be optimized for the proper design of adsorption systems. This study considers the optimization of kinetic data obtained for the removal of Pb(II) from aqueous solution by a tripolyphosphate modified kaolinite clay adsorbent. RESULTS: Modification of kaolinite clay with pentasodium tripolyphosphate increases its cation adsorption capacity (CEC) and specific surface area (SSA) from 7.81 to 78.9 meq (100 g)^?1 and 10.56 to 13.2 m² g^?1 respectively. X‐ray diffraction patterns for both unmodified and tripolyphosphate‐modified kaolinite clay suggest the modification is effective on the surface of the clay mineral. Kinetic data from the batch adsorption of Pb(II) onto the tripolyphosphate‐modified kaolinite clay adsorbent were optimized to a two‐stage batch adsorption of Pb(II) using the pseudo‐second‐order kinetic model. Mathematical model equations were developed to predict the minimum operating time for the adsorption of Pb(II). Results obtained suggest that increasing temperature and decreasing percentage Pb(II) removal by the adsorbent enhanced operating time of the adsorption process. The use of two‐stage batch adsorption reduces contact time to 6.7 min from 300 min in the single‐stage batch adsorption process for the adsorption of 2.5 m³ of 500 mg L^?1 Pb(II) under the same operating conditions. CONCLUSION: Results show the potential of a tripolyphosphate‐modified kaolinite clay for the adsorption of Pb(II) from aqueous solution and the improved efficiency of a two‐stage batch adsorption process for the adsorption of Pb(II) even at increased temperature. Copyright © 2009 Society of Chemical Industry     

Quantitative effects of synthesis conditions on oil absorptive properties of oil gels based on EPDM/4‐tert‐Butylstyrene

The oil absorption properties of porous polymeric gels are dependent on their synthesis conditions. In this work, we have investigated whether it is feasible to find a quantitative relationship between the synthesis conditions of porous poly(EDPM/4‐tert‐Butylstyrene) gels and their behavior in the kerosene absorption through a factorial design of experiments. For this purpose, a series of such oil gels have been synthesized in toluene with various divinylbenzene (DVB) and EPDM contents. The kerosene absorbency and kerosene‐absorption kinetics of oil gels were determined. Finally, empirical models correlating the synthesis conditions with the kerosene absorbency (Q_eq) and kerosene‐absorption kinetic constant (K) were calculated; it was observed that lower the DVB concentration and higher the EPDM fraction in the monomeric mixtures, the higher the kerosene absorbency. With regard to the kerosene‐absorption kinetics, the largest K value was achieved with the lowest DVB concentration and the highest EPDM fraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of thermoreactive polysiloxanes with cyclic fragments in the side chain

The synthesis of polysiloxanes with pendant unsaturated cyclic fragments have been successfully performed by hydrosilylation reactions of polymethylhydrosiloxane with 4‐vinyl‐1‐cyclohexene in the presence of platinum hydrochloric acid (0.1 M solution in THF), Karstedt's catalyst (Pt₂[(VinSiMe₂)₂O]₃) and platinum on the charcoal (5%). Reactions were carried out at various temperatures with different ratios of initial compounds. It was shown, that not all active ≡Si? H groups take part in the hydrosilylation reaction. Some kinetic parameters of reactions were studied. The synthesized oligomers were characterized by FTIR, ¹H, ¹³C, H,H‐COSY, and C,H‐correlation NMR spectroscopy. Calculations using the quantum‐chemical semi empirical AM1 method for modeling reactions between methyldimethoxysilane [Me(MeO)₂SiH] and 4‐vinyl‐1‐cyclohexene were performed to evaluate possible reaction paths. Synthesized oligomers were characterized by gel‐permeation chromatography, differential scanning calorimetric, thermogravimetric, and wide‐angle X‐ray analyses. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structural development Of TMMA and SSQXN‐8 as porous chelating resins

Superfast kinetics of Nd⁺³, Eu⁺³, and Gd⁺³ ions were studied on the surfaces of N,N,N^\,N^\‐tetramethylmalonamide (TMMA) and silsesquioxane (SSQXN‐8) resins. TMMA and SSQXN‐8 were prepared by suspension polymerization and sol–gel routes, respectively. They were identified using elemental analysis, FTIR, H‐NMR, ¹³C‐NMR, MIP, and BET surface area. Kinetic investigations were performed in batch conditions and different models were used to fit the data; Boyd and Helfferich models were found the best. The diffusion of the ions through the resins were very fast and found to be in the order of 10^?16 m²/S. Effective diffusions of the studied ions were found to be 10^?15 order of magnitude and directly proportional to the kinetic energy of the transition state. ΔS* values from ?166.044 to ?179.297 J mol^?1 K^?1 were estimated as entropy stability factors of the system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In situ activated 3,5-dinitrobenzoic acid covalent attached to nanostructured platform for NADH electrooxidation

The activation of 3,5-dinitrobenzoic acid (3,5-DNBA) in situ is proposed for electrocatalytic detection of NADH at low overpotentials. Thus, 3,5-DNBA was strategically connected to a nanostructured surface based on MWCNTs and PEI (an amine rich polymer). Then, R–NO/R–NHOH was electrogenerated in situ by cycling the potential between 0.15 and −0.55 V versus SCE. The formation of an intermediate charge transfer complex is proposed for the reaction between NADH and redox mediator. The apparent Michaelis–Menten constant (K_M) obtained by RDE voltammetry and amperometry was in good agreement, around 10⁻⁵ mol L⁻¹. The k_obs for the catalytic reaction evaluated by chronoamperometry and RDE voltammetry, was in good agreement and was found to be around 10⁴ L mol⁻¹ s⁻¹. The sensor provides a linear response range for NADH from 4.0 up to 42.0 μmol L⁻¹ with a sensitivity of 71 nA L μmol⁻¹, detection and quantification limits of 1.2 and 4.0 μmol L⁻¹ respectively, with a response time of 0.16 s.