Adsorption of phenthoate and acetochlor from water by clays and organoclays

Adsorption of phenthoate and acetochlor onto kaolin, montmorillonite, bentonite clays and respective organoclays prepared by the exchange of quaternary ammonium as tetradecyltrimethyl ammonium bromide(TTAB), dodecyltrimethylammonium bromide(DTAB), and cetylpyridinium chloride(CPC) were studied. The adsorption equilibrium data points were fitted to Freundlich isotherm equations. The adsorption of phenthoate and acetochlor were significantly enhanced by surfactant treatment of the clays. The amount of both pesticides adsorbed per unit mass of organoclay followed the order of TTA-kaolin < TTA-montmorillonite < TTA-bentonite, which is inconsistent with the organic carbon content of the clays. The removal efficiency of organomontmorillonite to treat acetochlor is in the order of CP(C 16 )-montmorillonite > TTA(C 14 )-montmorillonite > DTA(C 12 )-montmorillonite. Phenthoate is adsorbed to greater extent than acetochlor by each adsorbent, which may be due to the higher hydrophobicity of phenthoate, indicating considerable hydrophobic interaction between adsorbent/adsorbate systems.

Facile Method for the Synthesis of Copper Nanoparticles Supported on the Organoclay Material

In this study, synthesis of copper nanoparticles was performed using organoclay as a support to stabilize the nanoparticles. Organoclay amount was gradually increased, which had an effect on the morphology of the resultant nanoparticles. Low amount of organoclay added resulted in larger and agglomerated copper nanoparticles whereas increased amount of organoclay gave smaller sized nanoparticles. The hybrid materials were characterized using the SEM and TEM for morphology, XRD and FT-IR spectroscopy for structural elucidation, thermal analysis using TGA and also studying their antibacterial effect on the two well-known gram negative bacteria of E. coli and P. Aeruginosa. The synthesized nanoparticles were found to be crystalline Cu nanoparticles with a mix of CuO. Larger sized copper nanoparticles and agglomerates showed the higher thermal behaviour as compared with smaller nanoparticles with higher organoclay loading. The hybrid showed an improved antibacterial activity as compared with organoclay alone. The hybrid showed the higher antibacterial effect against the P. aeruginosa microorganism as compared with the E. coli microorganism.

Effect of Cosolvent in a Nucleophilic Substitution Reaction Using Organoclay in Triphase Catalytic System

A remarkable rate enhancement technique has been devised for a typical nucleophilic displacement reaction by using triphase catalytic materials based on tetraoctylammonium exchange forms of hectorite clay. Pseudo-first order rate constants (kobs) for the conversion of 1-bromobutane to the corresponding chloride under triphase conditions using the clay catalyst in the presence of various polar cosolvents have been observed. The results here have shown that the addition of a cosolvent increases the catalytic activity of the triphase system by several fold. In addition, the results have demonstrated that each cosolvent has a unique concentration for achieving an optimum reaction rate.

MORPHOLOGY AND PERFORMANCE OF UNSATURATED POLYESTER NANOCOMPOSITES MODIFIED WITH ORGANOCLAY AND THERMOPLASTIC POLYURETHANE

Unsaturated polyester（UPR）/thermoplastic polyurethane（TPU）/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy（SEM） and transmission electron microscopy（TEM）.The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.

XRD study of intercalation in statically annealed composites of ethylene copolymers and organically modified montmorillonites.2.One-tailed organoclays

Ethylene copolymers with different polar comonomers,such as vinyl acetate,methyl acrylate,glycidyl methacrylate,and maleic anhydride,were used for the preparation of polymer/clay nanocomposites by statically annealing their mechanical mixtures with different commercial or home-made organically modified montmorillonites containing only one long alkyl tail.The nanostructure of the products was monitored by X-ray diffraction,and the dispersion of the silicate particles within the polymer matrix was qualitatively evaluated through microscopic analyses.The effect of the preparation conditions on the structure and the morphology of the composites was also addressed through the characterization of selected samples with similar composition prepared by melt compounding.In agreement with the findings reported in a previous paper for the composites filled with two-tailed organoclays,intercalation of the copolymer chains within the tighter galleries of the one-tailed clays occurs easily,independent of the application of a mechanical stress.However,the shear-driven break-up of the intercalated clay particles into smaller platelets(exfoliation)seems more hindered.A collapse of the organoclay interlayer spacing was only observed clearly for a commercial one-tailed organoclay-Cloisite®30B–whereas the same effect was almost negligible for a home-made organoclay with similar structure.

Characterization of the Natural and Organomodified Clay Soil of Moukosso (Republic of Congo) by Dimethylsulfoxide: Application to the Adsorption of Lead (II) in Aqueous Solution

In this study, the authors characterized the raw clayey soil of Moukosso and modified by dimethylsulfoxide (DMSO) by several analytical methods, namely: X-ray diffraction (XRD), Fourier transform infrared (FTIR) and gravimetric thermal analysis (TGA). The cation exchange capacity (CEC) was also determined. Mineralogical analysis by XRD revealed the presence of muscovite (29.7%), kaolinite (8.9%), anatase (2.4%) and quartz (58.9%). The characterization of the organo-clay by infrared and by thermogravimetric analysis confirmed the intercalation of DMSO by the presence of vibration bands at 1008 cm-1 and 1070 cm-1 and a strong increase in the loss of mass. The cation exchange capacity of the raw material is 7.4 meq/100g. Rapid adsorption of Pb2+ ions was observed between 5 and 15 minutes of stirring time in both cases (raw clay and organomodified clay). The modeling of the isotherms by the models of Langmuir and Freudlich showed that these are of type S with a maximum amount of adsorption of 22.471 mg/g for the fine fraction and 41.493 mg/g for the clay intercalated with DMSO. Langmuir’s model best reproduces the experimental data of this study.

Environmental Properties of Minerals and Contaminants Purified by the Mineralogical Method

The investigation of the environmental properties of minerals, i.e., environmental mineralogy, is a branch of science dealing with interactions between natural minerals and spheres of the Earth surface as well as a reflection of global change, prevention of ecological destruction, participation in biomineralogy, and remediation of environmental pollution. Pollutant treatment by natural minerals is based on the natural law and reflects natural self-purification functions in the inorganic world, similar to that of the organic world - a biological treatment. A series of case studies related to natural self-purification, which were mostly completed by our group, are discussed in this paper. In natural cryptomelane there is a larger pseudotetragonal tunnel than that formed by [MnO6] octahedral double chains, with an aperture of 0.462-0.466 nm2, filled with K cations. Cryptomelane might be a real naturally-occurring mineral of the active octahedral molecular sieve (OMS-2). CrⅥ-bearing wastewater can be treated by natural pyrrhotite, which is used as a reductant to reduce CrⅥ and as a precipitant to precipitate CrⅢ simultaneously. Batch experiments were conducted using the CTMAB-Montmorillonite as an adsorbent for aromatic contaminants (phenol, aniline, benzene, toluene and xylenes), which are detected frequently in the leaching water from municipal waste deposits around China. The CTMAB modification has proved very effective to enhance the adsorption capacity of the sorbent. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside briquettes, and thus brings enough oxygen for combustion and the sulfation reaction. Effective combustion of the original carbon reduces the amount of dust in the fly ash.

Extraction Methods of Cyanotoxins Aqueous Media and Sediments

Cyanotoxins are chemical compounds produced by cyanobacterial mats grown in aquatic ecosystems. These may threaten human health and aquatic organisms. Extraction of these toxins is usually associated with many difficulties due to their concentration in aquatic ecosystems. This study is designed to provide suitable and effective extraction procedures that can effectively extract low concentration cyanotoxin from water and bacterial cells. The methodology is based on collecting raw material of cyanobacterial mats from naturally growing sites such as Wadi Gaza along with 16 liters of aquatic surrounding media. The materials were left in the Lab for 24 - 48 h for stabilization of the mats. The floating mats were collected using special funnel and allowed to air drying. The aqueous phase was extracted by liquid/liquid extraction using solvent mixture (hexane + ethylacetate 10% w:w), and by liquid solid extraction using several types of organoclays complexes. The solid phase was extracted by acetone and ultrasonic device. Results showed some difficulties were associated with liquid/liquid extraction whereas effective and easy extraction procedures were obtained by liquid solid extraction using either organoclay complex or activated charcoal. In contrast combination of both solid materials did not show improvement in the extracted cyanotoxin. Thus we recommend the use of organoclays or activated charcoal separately for extracting cyanotoxin. Further improvement of extraction can be tailored by using a specific organoclay complex that has some similarity in the chemical structure between the pre-adsorbed organic cation to the clay mineral and the chemical structure of cyanotoxin.

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS: EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.

The biodiesel-based flat-rheology drilling fluid system

As the base oil of the current flat-rheology synthetic drilling fluid is high in cost and not renewable, the biodiesel-based flat-rheology drilling fluid with low-cost, environmental protection and renewable advantage was studied. Based on the optimization of raw materials, a cheap, environment-friendly biodiesel of soybean oil ethyl ester with good fluidity at low temperature was selected as the base oil. By selecting high oil-water ratio and introducing cationic surfactant into the auxiliary emulsifier, the thickening of biodiesel-based emulsion caused by hydrolysis and saponification after high-temperature aging was effectively eliminated. The organoclay prepared with cationic modifier of hexadecyl trimethyl ammonium chloride was used to improve the rheologic properties, stability and fluid loss of the drilling fluid while preventing low-temperature thickening. A flat-rheology modifier was synthesized with dimer fatty acid and cocoanut fatty acid diethanolamide, which could form strong network structure in the biodiesel-based drilling fluid to adjust effectively rheological properties of the drilling fluid. A biodiesel-based flat-rheology drilling fluid system with the density of 1.2 g/cm^(3) has been formulated which has constant rheology in the temperature range of 2-90 ℃, temperature tolerance of 160 ℃, seawater salinity tolerance of 5%, shale cuttings tolerance of 10%, and is environmentally friendly.

Rapid Method for Greywater Treatment and Their Potential Reuse in Agriculture

Greywater, a type of wastewater, may be hazardous to human health and ecosystems. Greywater is a large fraction of wastewater that needs adequate attention for remediation and reuse in the agricultural sector so that a part of the water problem can be sorted out. This study aims to develop a rapid method for greywater treatment and reuse in agriculture. A microfilter consisting of sand, clay, organo-clay, charcoal, and biochar was designed and tested for greywater treatments. Biological Oxygen Demand (BOD), Chemical Oxygen Demand (COD), Total Kjeldahl Nitrogen (TKN), Total Dissolved Salts (TDS), Electric Conductivity (EC), turbidity and pH values were measured before and after using the microfilter. Results showed tremendous removal efficiency of BOD, COD, TKN, by using the developed microfilter. The microfilter was also effective in treating and placing pH, EC and TDS in the acceptable range for suitable agricultural use. Using the treated greywater for irrigation in corn, tomato seedlings showed increased growth compared with the control group (plants irrigated with tap water). This microfilter treatment was economical, safe, easy to handle and easily applicable. These encouraging results suggest the application of this method in many countries for solving the water scarcity problem.

Functional Copolymer/Organo-MMT Nanoarchitectures.VIII.Synthesis,Morphology and Thermal Behavior of Poly(maleic anhydride-alt-acrylamide)-Organo-MMT Clays Nanohybrids

Functional copolymer–clay hybrids were synthesized by radical-initiated intercalative copolymerization of maleic acid (MA) and acrylamide (AAm) with 2,2’-azobis (2-methylpropionamidine) dihydrochloride as a water-soluble ionizable radical initiator in the presence of reactive (octadecyl amine (ODA)-MMT) and non-reactive (dimethyldodecyl ammonium (DMDA)-MMT) organoclays at 50oC in aqueous medium under nitrogen atmosphere. The monomers was dissolved in aqueous medium, as well as both used clay particles were easily dissolved and dispersed with partially swollen in deionized water, respectively. Structure, thermal behavior and morphology of the synthesized nanocomposites were investigated by FTIR, XRD, DSC-TGA, SEM and TEM analysis methods, respectively. It was demonstrated that intercalative copolymerization proceed via ion exchange between organoclays and carboxylic groups of monomers/polymers which essentially improved interfacial interaction of polymer matrix and clay layers through strong H-bonding. In case of intercalative copolymerization in the presence of ODA-MMT clay, similar improvement was provided by in situ hydrogen-bonding and amidolysis of carboxylic/anhydride groups from copolymer chains with primary amine group of ODA-MMT. The nanocomposites exhibit higher intercalation/exfoliation degree of copolymer chains, improved thermal properties and fine dispersed morphology.

EFFECT OF SURFACE MODIFICATION OF MONTMORILLONITE ON THE PROPERTIES OF RIGID POLYURETHANE FOAM COMPOSITES

This study investigated the influence of various organically modified montmorillonites （organoclays） on the structure and properties of rigid polyurethane foam （RPUF） nanocomposites. The organoclays were modified with cetyltrimethyl ammonium bromide （CTAB）, methyl tallow bis（2-hydroxyethyl） quaternary ammonium chloride （MT2ETOH） and tris（hydroxymethyl）aminomethane （THMA） and denoted as CMMT, Cloisite 30B and OMMT, respectively. MT2ETOH and THMA contain hydroxyl groups, while THMA does not have long aliphatic tail in its molecule. X-ray diffraction and transmission electron microscopy show that OMMT and Cloisite 30B can be partially exfoliated in the RPUF nanocomposites because their intercalating agents MT2ETOH and THMA can react with isocyanate. However, CMMT modified with nonreactive CTAB is mainly intercalated in the RPUF matrices. At a relatively low filler content, the RPUF/CMMT composite foam has a higher specific compressive strength （the ratio of compressive strength against the apparent density of the foams）, while at relatively high filler contents, RPUF/Cloisite 30B and RPUF/OMMT composites have higher specific compressive strengths, higher modulus and more uniform pore size than the RPUF/CMMT composite.

SBR COMPOSITES REINFORCED WITH N-ISOPROPYL-N'PHENYL-P-PHENYLENEDIAMINE-MODIFIED CLAY

SBR compounds including the N-isopropyl-N＇-phenyl-p-phenylenediamine-modified clay（organoclay） were prepared.Effects of modified clay and antioxidant（IPPD） contents on mechanical and rheological properties of SBR composites were studied.FTIR results confirmed that the clay was chemically modified by IPPD and changed into an organoclay.X-ray diffraction（XRD） results confirmed the increase in interlayer distance of the clay due to the insertion of IPPD.Rheological and cure characteristics of SBR compounds were determined using RPA（Rubber Process Analyzer） and rheometer.Scorch time and cure time of SBR compounds decreased with introduction of the organoclay.Mechanical properties and heat aging resistance of the SBR composites were improved significantly by incorporation of the organoclay.

Enhancing the Adsorption Capacity of TMA-montmorillonite Toward HOCs

Organoclays synthesized with small organic cations can effectively adsorb hydrophobic organic compounds (HOCs), and the hydrophobic siloxane surfaces of clay minerals have been considered as the main adsorption sites for HOCs. Therefore, reducing charge density of clay minerals which can effectively increase the exposed siloxane surface areas has been generally used to enhance the adsorption capacity of organoclays towards HOCs. In this work, we will present a new method to increase the exposed siloxane surface areas of the synthesized organoclays and enhance their adsorption capacity. Firstly, the original inorganic cations on montmorillonite were exchanged with Li+, and then part of the Li+ (i.e., 20% to 60% of the montmorillonite’s CEC) were further exchanged with tetramethylammonium cation (TMA). After that ,the samples were heated at 200 ℃ for 12 h to make sure most of the Li+ were transferred to montmorillonite layers. With this method the layer charge of montmorillonite can be effectively reduced while the layered structure of montmorillonite will be preserved by pre-exchanged TMA. Finally, the remaining Li+ cations were further exchanged with TMA. The structural and adsorptive characteristics of the resulting organoclays were compared with those synthesized using traditional method (i.e., first reducing the charge density and then exchanging TMA).