A. Milutinović-Nikolić

Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta.

Phenol determination on HDTMA-bentonite-based electrodes

The partial and complete substitution of cations in the interlayer region of clay with different amounts of hexadecyl trimethylammonium bromide (HDTMABr) was performed. The aim was to synthesize organo-bentonites to be used as constituents of porous electrodes for the electrooxidation of phenol. Domestic clay from Bogovina was subjected to a common procedure of the production of organo-bentonites. It included the following steps: grinding, sieving, Na-exchange, cation exchange and drying. The samples were characterized by X-ray diffraction (XRD) analysis, while the textural properties were evaluated by nitrogen physisorption. The multisweep cyclic voltammetry was applied to analyze the behavior of the clay modified glassy carbon electrode. The influences of the surfactant loading and pH of the support electrolyte were investigated. Rapid deactivation of electrodes occurred in an acidic environment, while good stability of the investigated electrodes was obtained in alkaline medium.

Efficient stabilization of Saccharomyces cerevisiae external invertase by immobilisation on modified beidellite nanoclays.

The external invertase isoform 1 (EINV1) was immobilised on eight differently modified beidellite nanoclays. Modifications were composed of organo-modification with different amounts of surfactant - hexadecyl trimethylammonium cation (HDTMA), pillaring with Al/Fe containing polyhydroxy cations and acid modification of Na-enriched and pillared clays. The modified nanoclays were characterised by XRD, N2-physisorption, SEM and FT-IR spectroscopy. The amount of bound enzyme activity was significantly influenced by the modification of beidellite ranging from 50 to remarkable 2200U/g. Biochemical characterization was performed for five modified nanoclays showing the highest enzyme activity after invertase immobilisation. The investigation demonstrated that after immobilisation the structure and the catalytic properties of invertase were preserved, while Km values were slightly increased from 26 to 37mM. immobilisation significantly improved thermal and storage stability of EINV1. Results indicate that beidellite nanoclays obtained by low cost modifications can be applied as a suitable support for the immobilisation of invertase. The immobilizate can be efficiently engaged in sucrose hydrolysis in batch reactor.

Synergic adsorption of Pb2+ and reactive dye--RB5 on two series of organomodified bentonites.

Two series of organobentonites (OBs) were synthesized from Na(+)-exchanged bentonite clay from Bogovina, Serbia. In the first series the starting material was modified using hexadecyltrimethylammonium (HDTMA(+)) ion in the amounts corresponding to 0.2, 0.5, 1.0 and 2.0 of the CEC value. The second series was obtained using quaternary alkyl ammonium cations (QAACs) with different alkyl chain lengths: hexadecyltrimethylammonium (HDTMA(+)), dodecyltrimethylammonium (DDTMA(+)) and tetramethylammonium (TMA(+)) ions. The synthesized OBs were characterized. The adsorption of anionic reactive dye Reactive Black 5 (RB5) and Pb(2+) from single component solutions and their bi-component solution was investigated for both series of OBs. The adsorptive properties of the OBs were correlated to the amount and type of incorporated QAACs. The correlation was tested using different mathematical models and best fits were found. Experimental results showed that simultaneous adsorption of RB5 and Pb(2+) exhibited synergic effect. The adsorption capacity for both RB5 and Pb(2+) was higher in their bi-component solution than in single-component solutions. These results indicate the creation of new adsorption sites during the simultaneous adsorption.

The Influence of Acid Treatment on the Nanostructure and Textural Properties of Bentonite Clays

The nanostructure and textural properties of acid-activated bentonite clays from the Bogovina coalmine were investigated. The acid activation was performed with HCl in the concentration range 1.5-7.5 M. The atomic force microscopy followed by image analysis was used in order to establish the influence of the acid treatment on the size of bentonite particles. Nitrogen adsorption-desorption isotherms at -196 °C were used to estimate the specific surface area, pore volume and pore size distribution. The acid treatment reduces the size of bentonite particles and increases the specific surface area and pore volume of the investigated bentonites. These effects are improved by increasing the acid concentration up to 4.5 M HCl. Further increase in acid concentration does not result in development of new porous structure.

Toluene Degradation in Water Using AlFe-Pillared Clay Catalysts

Abstract The catalytic wet peroxide oxidation (CWPO) of toluene on two bentonite-based AlFe-pillared clays (PILCs) with different iron contents was investigated. The PILCs were obtained using bentonite clay from Bogovina, Serbia. The change in chemical and phase composition and textural properties of the starting clay and synthesized catalysts was monitored using X-ray diffraction, inductively coupled plasma optical emission spectrometry, UV-Vis diffuse reflectance spectrometry, and physisorption of nitrogen. The catalytic performance was examined using gas chromatography. The Na-exchange process lowered the (001) smectite basal plane spacing, but the clay retained its swelling properties, while the pillaring process increased it. The surface areas of both synthesized pillared clays increased to values although their Fecontent was different. At 37 °C, both catalysts show significant toluene degradation, with the one richer in Fe having higher efficiency. The leaching of the active cations during reaction was negligible, and the catalysts were stable. AlFe-pillared clay catalysts can be used in CWPO for the elimination of BTEX compounds from plant effluent streams.

p-NITROPHENOL ELECTRO-OXIDATION ON A BTMA+-BENTONITE-MODIFIED ELECTRODE

Phenol and its derivatives are regarded as ‘priority pollutants’ and p-nitrophenol (p-NP), in particular, is of great interest due to its toxicity and frequent presence in waste waters and fresh waters. Straightforward, inexpensive methods to identify p-NP in water, however, is lacking. In the present study, an electrochemical technique using clay-modified electrodes to measure p-NP was investigated as a potentially promising method to fill that gap. A glassy carbon electrode (GCE) was modified with a thin layer of Na-enriched bentonite and a series of benzyltrimethylammonium (BTMA+)-bentonites (BTMA+-B) in order to confirm these materials as p-NP electrosensitive. A series of organobentonites was synthesized using different BTMA+/bentonite ratios. The materials obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, and a low-temperature nitrogen adsorptiondesorption method. A monolayer arrangement of BTMA+ within the interlamellar region of beidellite-rich smectite was confirmed. Deterioration of the textural properties was observed with increase of BTMA+ loading. The electro-oxidation of p-NP in an acidic medium on BTMA+-B-modified GCE was investigated. The cyclic voltammetry method with a three-electrode cell was used. The reference electrode was Ag/AgCl in 3 M KCl and a Pt foil was the counter electrode. For each electrochemical measurement, a different BTMA+ loading in BTMA+-B was used as the material for GCE coating and applied as the working electrode. The electrochemical activity of BTMA+-B-based electrodes increased with BTMA+ loading. The results confirmed that the organophylic character of the BTMA+-B-modified surface was the main influence on the electrochemical activity of the BTMA+-B-based GCE; the influence of textural properties was almost negligible. The increased electrode activity toward p-NP was achieved by the adsorption of p-NP on the electrode surface, the process that commonly precedes the electro-oxidation. The present study showed that synthesized materials could potentially be used in an electrochemical test for the presence of p-NP in water solutions.

Optical fibers with composite magnetic coating

Abstract The goal of these investigations was to define the process parameters that enable the formation of a composite coating with the most uniform thickness on an optical fiber. The composite coating was obtained by drawing the optical fiber through a reservoir with a die at the bottom. The reservoir was supplied with a dispersion of magnetic powder in a polymer solution. The effect of the dispersion viscosity, powder concentration and drawing rate on the uniformity of the composite coating thickness under laboratory conditions was investigated on a defined system to establish the optimal coating conditions. Dispersions were formed by dispersing different concentrations of Ba-ferrite in a poly(ethylene-co-vinyl acetate) solution in toluene. The thickness of the coatings and its uniformity were determined by microscopic analysis and further evaluated by mathematical–statistical analysis. The smallest standard deviation (S.D.) of the mean value of the diameter of the optical fiber with a composite coating was chosen as the criteria for defining the most uniform composite coating. The results show that the most uniform coatings were obtained with a dispersion viscosity whose value was about 1.2 Pa s. All the process parameters should be established in accordance with this viscosity value, enabling the formation of the most uniform composite coating for the investigated system.

Textural properties of poly(glycidyl methacrylate): acid-modified bentonite nanocomposites

The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modified bentonite (BA) into the reaction system. All samples were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), mercury intrusion porosimetry, and low temperature physisorption of nitrogen. The FTIR and TEM analysis confirmed incorporation of BA into the copolymer structure and the successful formation of nanocomposites. TEM images confirmed formation of nanocomposites having both intercalated and exfoliated acid-modified bentonite in copolymer matrix. A significant increase of specific surface area, pore volume, and porosity of the nanocomposites in comparison to the copolymer were obtained. The difference between textural properties of nanocomposites with different amounts of incorporated acid-modified bentonite was less prominent.

Analysis of solid waste from ships and modeling of its generation on the river Danube in Serbia

This study focuses on the issues related to the waste management in river ports in general and, particularly, in ports on the river Danube’s flow through Serbia. The ports of Apatin, Bezdan, Backa Palanka, Novi Sad, Belgrade, Smederevo, Veliko Gradiste, Prahovo and Kladovo were analyzed. The input data (number of watercrafts, passengers and crew members) were obtained from harbor authorities for the period 2005–2009. The quantities of solid waste generated on both cruise and cargo ships are considered in this article. As there is no strategy for waste treatment in the ports in Serbia, these data are extremely valuable for further design of equipment for waste treatment and collection. Trends in data were analyzed and regression models were used to predict the waste quantities in each port in next 3 years. The obtained trends could be utilized as the basis for the calculation of the equipment capacities for waste selection, collection, storage and treatment. The results presented in this study establish the need for an organized management system for this type of waste, as well as suggest where the terminals for collection, storage and treatment of solid waste from ships should be located.