Partially exchanged organophilic bentonites

Phenol is a pollutant that has caused many problems even when present in low concentrations and still represents an environmental problem with difficult solution. This paper presents a study of phenol adsorption by organophilic clays, obtained from aVerde Claro bentonitic clay, from Bravo, Paraíba State, Brazil, at different partial cation exchange degrees with hexadecyltrimethylammonium (HDTMA) chloride, at increasing reacting ratios, from 20 to 120 mmol/100 g of clay, which were characterized in a previous paper. By using Freundlich isotherms obtained for each case, which presented the best correlation coefficients with experimental data, it can be seen that for equilibrium concentrations up to 0.53 mmol L⁻¹ of phenol, the adsorptive capacity decreases for organophilic bentonites obtained at cation exchange degrees higher than 80 mmol/100 g of clay. This indicates that in these cases, the higher is the exchange by organic cation, the higher is the difficulty for the phenol diffusion and sorption in the interlayer space of the organophilic clays. For higher equilibrium concentrations, the maximum adsorption occurs for the organophilic bentonite obtained at 100 mmol/100 g of bentonite exchange.     

Thermal stability and mechanical properties of sisal in cycle process

Differential thermal analysis (DTA) was the first thermal analysis technique used to qualitatively characterize natural clays and respective curves has been used since more than 60 years as their ‘fingerprint’. With the development of microprocessed equipments in the last decades, derivative thermogravimetric (DTG) curves also may be used for this purpose in some cases, which also may allow a quantitative characterization of clay components. TG and DTG curves are more indicated than DTA or DSC curves to identify and to better analyze the several decomposition steps of natural or synthetic organoclays. These questions are discussed in applications developed to characterize Brazilian kaolinitic clays, bentonites and organophilic clays.     

Organoclay sorption of benzene as a function of total organic carbon content

The sorption of benzene to bentonite, activated carbon, and two organo-clays synthesized with the quaternary ammonium organic cations hexadecyltrimethylammonium (HDTMA) and benzyltriethylammonium (BTEA) was quantified as a function of total organic carbon content. The unmodified bentonite sorbed no benzene, while the activated carbon exhibited the strongest benzene uptake. For the organoclays, organic cations were exchanged onto Wyoming bentonite at four different percentages of the clay's cation exchange capacity. For HDTMA clay, in which partitioning is the dominant sorptive medium, it was determined that benzene sorption increased as the total organic carbon content increased (as the clay became more hydrophobic). In contrast, the sorption of benzene to BTEA clay, an adsorptive clay, decreased as the total organic carbon content of the clay was increased. It is believed that the sorptive capacity of BTEA clay decreases due to the formation of positively charged dimers on the clay's surface that block access to the sorptive sites. The organoclays sorbed more benzene than the unmodified bentonite, but less than the activated carbon.     

Thermal decomposition kinetics of diethyl dithiocarbamate complexes of copper(II) and nickel(II)

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL₂ and NiL₂ (L^?=diethyl dithiocarbamate anion) in air are studied. The main decomposition temperature ranges are: For CuL₂, DTG 250–350°, DTA 300–320° and for NiL₂, DTG 290–390°, DTA 360–400°. Mass loss considerations at the main decomposition stages indicate conversion of the complex to sulphides. Mathematical analysis of TG data shows that first order kinetics are applicable in both cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.

     

Thermogravimetric study of <Emphasis Type="Italic">n</Emphasis>-alkylammonium-intercalated montmorillonites of different cation exchange capacity

Three n-alkylammonium salts of varying alkyl chain length were ion exchanged with montmorillonites (MMT) of different cation exchange capacity (CEC). The intercalated MMTs were characterized by thermogravimetry (TG), XRD, FTIR to acquire an insight into the intergallery structural arrangement of the organic alkylammonium cations (AAC). The increment in the intergallery spacing from XRD pattern was correlated with chain length and interlayer arrangement of AAC. Multiple organic mass-loss stages in thermogravimetric analysis indicate two types of anchorage of AAC in intercalated clay. CEC of MMT was found to influence the intergallery confinement and excess adsorption of AAC.     

Clay-catalyzed reactions of coagulant polymers during water chlorination

The influence of suspended clay/solid particles on organic–coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence.     

Sorption of nitroaromatic compounds to synthesized organoclays

This project quantifies the ability of seven engineered organoclays to sorb TNT and two of its reduction products: 2-amino-4,6-dinitrotoluene (2-A-4,6-DNT) and 4-amino-2,6-dinitrotoluene (4-A-2,6-DNT). The organoclays used in the TNT sorption studies were synthesized in the laboratory by combining bentonite with benzyltriethylammonium chloride (BTEA) at 50, 75, and 100% of the bentonite's cation exchange capacity and with hexadecyltrimethylammonium bromide (HDTMA) at 25, 50, 75, and 100% of the bentonite's cation exchange capacity. For sorption of 2-A-4,6-DNT and 4-A-2,6-DNT, two organoclays were tested: BTEA at 50% CEC and HDTMA at 75% CEC. Sorption data with HDTMA organoclay and TNT were fit to linear isotherms and demonstrated that the clay's sorptive capacity increased as the amount of total organic carbon exchanged onto the clay increased. Sorption data with BTEA organoclay and TNT were fit to Langmuir isotherms; however, the clay's sorptive capacity increased as the amount of total organic carbon sorbed to the clay's surface was decreased. Sorption behavior for TNT reduction products 2-A-4,6-DNT and 4-A-2,6-DNT to one HDTMA organoclay and one BTEA organoclay demonstrated that HDTMA organoclay at 10.3% total organic carbon was a more effective sorbent than BTEA organoclay at 5.2% total organic carbon.     

Adsorption of tartrazine from an aqueous solution by octadecyltrimethylammonium bromide-modified bentonite: Kinetics and isotherm modeling

A modified bentonite was prepared at different surfactant (ODTMA) loadings through ion exchange. The obtained organobentonite adsorbent materials were then used for the removal of an anionic dye, tartrazine, from an aqueous solution. The bentonite was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and Brunauer- Emmett-Teller (BET) method. The modification of organophilic bentonite by ODTMA increases the basal spacing d₀₀₁ from 24.1 to 39.1 Å when the cation exchange capacity increases from 1 to 4. The increase in the spacing, due to the basic organic modifications, was confirmed by the results of thermogravimetric analysis, Fourier transform infrared spectroscopy, and BET. The effects of contact time, initial concentration, and solution pH onto an adsorbed amount of tartrazine were investigated. To predict adsorption isotherm, the experimental data were analyzed using the Langmuir and Freundlich isotherm equations. It was determined that the isotherm data were fitted to the Langmuir isotherm. The adsorption process was also found to follow a pseudo-second-order kinetic model.     

TG studies of a composite solid rocket propellant based on HTPB-binder

Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E _a (activation energy) and A (pre-exponential factor) and the compensation parameter (S _p) were determined. The apparent activation energies obtained from different methods showed a very good agreement. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal Decomposition Kinetics of Some Metal Complexes of N,N-diethyl-n '-benzoylthiourea

Thermogravimetry (TG) and differential thermal analysis (DTA) were performed on the complexes with general formula (M(DEBT)_n (where M =Fe, Co, Ni, Cu or Ru; n =2, or 3 and DEBT=N,N-diethyl-N'-benzoylthiourea). Derivative thermogravimetric (DTG) curves were also recorded in order to obtain decomposition data on the complexes. The complexes of Fe(III), Co(II), Ni(II), Cu(II) and Ru(III) displayed two- or three-stage decomposition patterns when heated in a dynamic nitrogen atmosphere. Mass loss considerations relating to the decomposition stages indicated the conversion of the complexes to the sulfides or to the corresponding metal alone (Cu, Ru, NiS, CoS or FeS). Mathematical analysis of the TG and DTG data showed that the order of reaction varied between 0.395 and 0.973. Kinetic parameters such as the decomposition energy, the entropy of activation and the pre-exponential factor are reported. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Decomposition of Some Chemical Compounds Used As Food Preservatives and Kinetic Parameters of This Process

Thermal decomposition processes of selected chemicals used as food preservatives such as sodium formate, sodium propionate, sodium nitrates(V and III) and sodium sulphate(IV) were examined by the derivatographic method. Based on the curves obtained, the number of decomposition stages and characteristic temperatures of these compounds have been found. Mass decrements calculated from TG curves ranged from 28.9% for sodium formate to 77.8% for sodium nitrate(V), while sodium sulphate showed a mass increment of 5.6%. Kinetic parameters such as activation energy (E _a ), frequency factor (A ) and reaction order (n ) were calculated from TG, DTG and T curves. Sodium formate shows the highest values of E _a and A which amount to 171.7 kJ mol^–1 and 5.8⋅10¹⁴ s^–1 , respectively, while the lowest ones, E _a =28.2 kJ mol^–1 and A =3.65⋅10² s^–1 belong to sodium nitrate(V). This revised version was published online in August 2006 with corrections to the Cover Date.     

Impact of rock fabric,thermal behavior,and carbonate decomposition kinetics on quicklime industrial production and slaking reactivity

This paper deals with thermal analyses, burning trials and reactivity tests on 15 carbonate rocks, i.e., pure and impure carbonates, mud-supported and grain-supported limestones, crystalline marbles, and dolomites, used for the production of different lime products in industrial vertical shaft kilns worldwide. In particular, thermogravimetric and differential thermogravimetric analysis (TG–DTG) on massive (80–120 g) fine-grained (< 3.35 mm) samples allowed the extrapolation of the Arrhenius kinetic parameters, i.e., the (apparent) activation energy (E_a) and the pre-exponential or frequency factor (A). Other calcination parameters, i.e., the duration time, starting and ending calcination times and temperatures, and peaks of maximum calcination rate were also extrapolated in order to enhance their relationships with quicklime reactivity. Moreover, thermal analyses (TG–DTG–DTA) were repeated on powders (90 mg) using a more accurate analyzer to compare results. The study is completed by a thorough chemical–physical and mineralogical–petrographic characterization of carbonate rocks and derived burnt products. Results pointed out that medium-to-coarse crystalline materials, i.e., grain-supported limestones, diagenetic dolomites, and granoblastic marbles presented the highest activation energy, burnability and slaking reactivity. Conversely, microcrystalline carbonates with the highest micrite-to-sparite ratio, i.e., mud-supported limestones, and impure carbonates, enriched in quartz, clay minerals, and other subordinated non-carbonate impurities, presented the lowest activation energy, burnability, and slaking reactivity. This study also investigated the effect of BET-specific surface area and real density, depending on specific sintering tendency, on quicklime reactivity. Results from this multidisciplinary research activity put further constraints on carbonate rocks calcination kinetics and their suitability in the lime industry.

     

Thermal stability of ionene polymers

Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer–clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na⁺ and little Ca²⁺. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol^?1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol^?1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene.     

Thermal decomposition kinetics of Schiff base complexes of copper(II) and palladium(II)

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL₂ and Pd(LH)₂Cl₂ (LH=salicylidene-2-aminofluorene and 2-hydroxy-1-naphthalidene-2-aminofluorene) in air are studied. Mass loss considerations at the main decomposition stages indicate conversion of the complex to oxides. Mathematical analysis of TG data shows that first order kinetics are applicable in all cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.     

Calorimetric study and thermal analysis of [ErY(Ala)4(H2O)8](ClO4)6 (Ala=ALANINE)

A solid complex of rare-earth compounds with alanine, [ErY(Ala)₄(H₂O)₈](ClO₄)₆ (Ala=alanine), was synthesized, and a calorimetric study and thermal analysis for it was performed through adiabatic calorimetry and thermogravimetry. The low-temperature heat capacity of [ErY(Ala)₄(H₂O)₈](ClO₄)₆ was measured with an automated adiabatic precision calorimeter over the temperature range from 78 to 377 K. A solid-solid phase transition was found between 99 and 121 K with a peak temperature at 115.78 k. The enthalpy and entropy of the phase transition was determined to be 1.957 Kj mol^-1, 16.90 j mol^-1 k^-1, respectively. Thermal decomposition of the complex was investigated in the temperature range of 40~550°C by use of the thermogravimetric and differential thermogravimetric (TG/DTG) analysis techniques. The TG/DTG curves showed that the decomposition started from 120 and ended at 430°C, completed in three steps. A possible mechanism of the thermal decomposition was elucidated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation of natural rubber composites with addition of montmorillonite fillers using thermal analysis

This paper is devoted to the investigation of the properties of the natural rubber composites prepared using the cation exchanged-montmorillonite fillers. The characteristics of the montmorillonite fillers were studied by Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TG). These characterized fillers were used to preparation of the natural rubber composites, which were submitted to measurements of dynamic-mechanical thermal analysis (DMTA) and vulcanizing characteristics (M _H, M _L, t _s, t _c(90), R _v) as well as physico-mechanical properties (tensile strength, modulus at 300 elongation—M ₃₀₀, tensibility).     

Thermal studies on some organotin(IV) complexes with piperidine and 2-aminopyridine dithiocarbamates

The complexes of piperidine dithiocarbamate, 2-aminopyridine dithiocarbamate and organotin(IV) of the type R₃Sn(L¹), R₂Sn(L¹)₂, R₃Sn(L²), R₂Sn(L²)₂, [R=C₆H₅CH₂ (benzyl), p-ClC₆H₄CH₂ (p-chlorobenzyl), L ¹=sodium piperidine dithiocarbamate and L ²=sodium 2-aminopyridine dithiocarbamate] have been synthesised and characterised by spectral studies (IR, UV, ¹H NMR). Thermogravimetric (TG) and differential thermal analytical (DTA) studies have beeen carried out for these complexes and from the TG curves, the order and apparent activation energy for the thermal decomposition reactions have been elucidated. The various thermal studies have been correlated with some structural aspects of the complexes concerned. From DTA curves, the heat of reaction has been calculated.     

Thermal analyis of hexadecyltrimethylammonium–montmorillonites

Na-montmorillonite (Na-MONT) was loaded with hexadecyltrimethylammonium cations (HDTMA) by replacing 41 and 90% of the exchangeable Na with HDTMA, labeled OC-41 and OC-90, respectively. Na-MONT, OC-41, and OC-90 were heated in air up to 900 °C. Unheated and thermally treated organoclays heated at 150, 250, 360, and 420 °C are used in our laboratory as sorbents of different hazardous organic compounds from waste water. In order to get a better knowledge about the composition and nature of the thermally treated organoclays Na-MONT and the two organo-clays were studied by thermogravimetry (TG) in air and under nitrogen. Carbon and hydrogen contents in each of the thermal treated sample were determined and their infrared spectra were recorded. The present results showed that at 150 °C both organoclays lost water but not intercalated HDTMA cations. At 250 °C, many HDTMA cations persisted in OC-41, but in OC-90 significant part of the cations were air-oxidized into H₂O and CO₂ and the residual carbon formed charcoal. After heating both samples at 360 °C charcoal was present in both organo clays. This charcoal persisted at 420 °C but was gradually oxidized by air with further rise in temperature. TG runs under nitrogen showed stepwise degradation corresponding to interlayer water desorption followed by decomposition of the organic compound, volatilization of small fragments and condensation of non-volatile fragments into quasi-charcoal. After dehydroxylation of the clay the last stages of organic matter pyrolysis and volatilization occurred.     

Kinetic and thermodynamic parameters of the thermal decomposition of zinc(ii) dialkyldithiocarbamate complexes

The thermodynamic and kinetic parameters of the thermal decomposition of Zn(S₂CNR₂)₂ complexes (R=CH₃, C₂H₅ and n-C₃H₇) were determined with the dynamic thermogravimetric method. Superimposed TG/DTG/DSC curves show that thermal decomposition reactions for chelates with R=C₂H₅ and n-C₃H₇ occur in the liquid phase, at temperatures far away from their melting points, whereas for the complex with R=CH₃ the thermal decomposition begins at a temperature closer to its melting point, suggesting a rather complex decomposition mechanism. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effects of organophilic clay on the solvent‐maintaining capability,dimensional stability,and electrochemical properties of gel poly(vinylidene fluoride) nanocomposite electrolytes

Four quaternary alkyl ammonium salts were used in an organophilic procedure, performed on montmorillonite clay, and resulted in intercalation in dimethylformamide (DMF) or ethylene carbonate (EC)/propylene carbonate (PC) as a cosolvent between poly(vinylidene fluoride) (PVdF) and the organophilic clay. An examination using X‐ray diffraction revealed that PVdF entered galleries of montmorillonite clay, and it exhibited exfoliation and intercalation phenomena when it was analyzed with transmission electron microscopy. Gel PVdF nanocomposite electrolyte materials were successfully prepared by the addition of the appropriate percentages of DMF or PC/EC as a cosolvent, organophilic clay, and lithium perchlorate to PVdF. The maximum ionic conductivity was 1.03 × 10^?2 S/cm, and the materials exhibited better film formation, solvent‐maintaining capability, and dimensional stability than electrolyte films without added organophilic clays. The results of cyclic voltammetry testing showed that the addition of the organophilic clays significantly enhanced the electrochemical stability of the polymer electrolyte system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3873–3882, 2002