Molecular modeling of polymer-clay nanocomposite precursors: Lysine in montmorillonite interlayers

The layered structure of clays with interlayer cations leads to unique chemical and mechanical properties, which have been capitalized on in the field of polymer/layered silicate nanocomposites. Hydrophilic silica surfaces can become organophilic with the inclusion of alkylammonium cations, which improve the wetting characteristics of the polymer matrix. In fact, the molecular level interactions of amino acids, either natural or non-natural, with clay surfaces are at the heart of fields of study as diverse as nanocomposites fabrication, drug delivery, bio-remediation of soils and catalysis of biological polymers, to name a few. The ubiquity of these systems and the potential uses to which they could be put suggests the necessity of a deeper understanding of the interplay of bonds, conformations, and configurations between the molecules and the hosts. The interactions of the amino acid lysine with sodium montmorillonite were studied using theoretical molecular modeling methods. The interlayer spacing of montmorillonite was increased by incorporating water molecules and allowing the system to evolve with molecular mechanics. Care was taken to retain the sodium cations in the interlayer. The initial amino acid conformation was obtained surrounding the molecule with numerous discrete water molecules and minimizing the system at the semi empirical level. The optimized amino acid was then placed in the interlayer space in a series of initial positions. Molecular mechanics calculations were performed and the final positions were analyzed. The results tended to indicate the preponderance of configurations which included surface-sodium-amino acid complexes with a variety of spatial arrangements. These results were compared with molecular dynamics calculations of similar systems from the literature.     

Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.     

The adsorption of CaOH+ on (001) basal and (010) edge surface of Na‐montmorillonite: a DFT study

Ca²⁺ cations were generally added to facilitate the coagulation of stable fine clay mineral dispersion due to the specific adsorption of their first hydrolysis CaOH⁺ species at pH near 10. The adsorption of CaOH⁺ on dry and hydrated (001) basal surface and (010) surface of Na‐montmorillonite was investigated by using density functional theory method combined with the periodic slab model method. The adsorption energies and geometries, Mulliken charge, electron density difference, and density of state were presented and discussed. It was found that the adsorption energy of CaOH⁺ on (010) edge surface of Na‐montmorillonite (?328.8 kJ/mol) was much larger than that (?126.9 kJ/mol) on (001) basal surface. The presence of waters could increase the adsorption energy of CaOH⁺ on (001) surface but affect that on (010) surface slightly. The protons in Si–OH and Al–OH₂ groups as well as the OH₂ ligands in Al–OH₂ group on (010) edge surface were easily dissociated and coordinated to CaOH⁺ to form new waters. CaOH⁺ was the most steady adsorption species among CaOH⁺, Ca²⁺ cation, and H₂O molecule on both (001) and (010) surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Enthalpies of adsorption of methylene blue and crystal violet to montmorillonite

Calorimetric measurements of the enthalpy of adsorption on montmorillonite indicate different patterns for methylene blue (MB) and crystal violet (CV). The enthalpy of adsorption of MB is endothermic up to 73% of the cation exchange capacity (CEC) (i.e., about 0.6 mmol g^-1 clay), whereas at higher adsorption ratios the adsorption reaction becomes exothermic. The enthalpy of adsorption of CV is exothermic for all amounts adsorbed. These results were confirmed with adsorption experiments that prove that adsorption of MB increase with temperature, whereas CV adsorption decreases. This behavior indicates changes in the equilibrium coefficient according to Van't Hoff's equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Adsorption of fast green and erythrosin-B to montmorillonite modified with crystal violet

Adsorption of erythrosin-B (EB) and fast green (FG) to a non-charged organosmectite based on crystal violet adsorbed up to 100% of the cation exchange capacity (CEC) was tested. Adsorption isotherms of EB and FG were prepared at 3, 24 and 50°C. All isotherms are of H-type reaching loads of approximately up to 20% of the original CEC of the crude montmorillonite (up to 0.15 and 0.10 mol dye kg^–1 clay for EB and FG, respectively). Adsorption decreases with temperature, indicating an exothermic process. Enthalpy was evaluated using van’t Hoff equation, yielding approximately –20 kJ mol^–1 for both dyes.     

Differential thermal analysis of montmorillonite

The paper provides an overview of publications on the DTA of montmorillonites (in the temperature range 20–1100°C), starting with the first experiments of Le Chatelier (1887) and ranging up to the present. Consideration is given to the dehydration, dehydroxylation, amorphization and rehydration of montmorillonite (42 references).     

Nitration of phenolic compounds by metal-modified montmorillonite KSF

The nitration of phenolic compounds with 60% nitric acid (1.2 equiv) has been carried out in the presence of metal-modified montmorillonite KSF, prepared from different metals (V, Mo, W; Sc, La, Yb, Eu, In, Bi, Ti, Zr, Hf) and KSF or nitric acid treated HKSF, as catalysts. These catalysts showed good stabilities and high catalytic activities in nitration process. In addition, these catalysts can be recovered easily and reused for many times in nitration. This process is an eco-safer and environment-benign way for clean synthesis of nitrated phenolic compounds.     

Role played by the head size of some non‐ionic surfactants on their adsorption onto montmorillonite clay

Sorption behavior of polyoxethylene(n)monooleate series [Ol(EO)_n] onto montmorillonite clay was studied at 25°C to investigate the influence of the surfactant's head size on the sorption process. All the tested surfactants exhibited L‐shaped isotherms that means a strong interaction between the adsorbent and the adsorbate. Also, all the obtained isotherms ended with a drastic increase in the isotherm slope at nearly constant equilibrium concentration. This abrupt increase reflected the fairly high affinity of the tested surfactants to the clay surface at high bulk concentration region. The maximum amount adsorbed at the plateau region, Γ_max, was calculated according to the Langmuir adsorption theory and followed the order: Ol(EO)₁₄ > Ol(EO)₂₀ < Ol(EO)₄₀ < Ol(EO)₈₀. In case of short ethylene oxide (EO) chain, Γ_max decreased with the increase in the chain length; but a reverse result was obtained in case of surfactants with longer EO chain length (20 to 80 units). The free energy of adsorption, ΔG°_ad, had negative values indicating the spontaneous adsorption of surfactant molecules onto clay. The values of ΔG°_ad increased with increasing EO units from 14 to 20 units and decreased with further elongation in the EO chain from 20 to 80 units. Copyright © 2004 John Wiley & Sons, Ltd.     

Adsorption of Cu(II) in aqueous solution by sodium dodecyl benzene sulfonate-modified montmorillonite

The pristine montmorillonite (P-Mt) was modified with sodium dodecyl benzene sulfonate (SDBS) to form SDBS montmorillonite (SDBS-Mt) for the purpose of enhancing the removal performance of Cu(II) from aqueous solution. The materials were characterized by means of XRD, SEM-EDS, BET, and FTIR to analyze the surface morphology and structure. SDBS-Mt displayed a higher adsorption capacity than P-Mt. The adsorption kinetic model and the adsorption isotherm model are depicted by the pseudo-second-order kinetic equation and the Langmuir equation, respectively. The adsorption of Cu(II) on SDBS-Mt is a spontaneous and endothermic process. The order of influence of coexisting cations on the adsorption of Cu(II) is Ni(II) > Co(II) > Zn(II). In addition, the adsorbent has great regeneration performance after five cycles of regeneration. The main mechanisms of Cu(II) adsorption by SDBS-Mt may include electrostatic attraction, ion exchange, and complexation of sulfonate groups. In brief, SDBS-Mt may be a promising, simple, and low-cost adsorbent for the treatment of Cu(II) in aqueoussolutions.     

Structure and properties of polymer modified TiO2 pillared montmorillonite

With the aim of improving the microstructures and properties of TiO₂ pillared montmorillonite (MMT), a long-chain polymer (polyoxypropylenediamine, PPO-D 2000) was used as a template to synthesize composite pillared MMT. The materials were characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectrophotometer, Fourier Raman (FT-Raman) spectrophotometer, thermo-gravimeter/differential thermogravimeter (TG/DSC), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) methods. The results show that as compared to low-molecular weight surfactant, this polymer significantly expanded the interlayer spacing and thus more TiO₂ could be intercalated into MMT. The specific surface area of polymer/TiO₂ pillared MMT was increased by 13% with comparison to TiO₂ pillared MMT and rose to 241.52 m²/g. Both the pore diameter and volume are doubled, and thus the pore structure is optimized markedly. The investigation on the photo-catalytic degradation of methyl orange in aqueous solution show that the modulation of polymer molecules raise the adsorption content of montmorillonite and improve the photo-catalytic activity. Therefore, this process provides a novel alternative to design and prepare the advanced eco-catalytic materials with high adsorption capacity and photo-catalytic activity. __________ Translated from Huaxue Tongbao, 2007, 12: 936–941 [译自: 化学通报]     

Efficient iodination of aromatic compounds using potassium ferrate supported on montmorillonite

Potassium ferrate impregnated on montmorillonite is a mild,cheap,and non-toxic reagent for the iodination of phenols, including naphthol,aromatic amines,and heterocyclic substrates in fair to excellent yields by a simple isolation procedure.     

Reversible Lithium Insertion into LiNb6Cl19

Crystals of LiNb₆Cl₁₉ were obtained as black needles by solid state reaction of Nb powder, NbCl₅, and Li₂C₂ at 530 °C. The structure contains ladder‐like motifs built of edge and face sharing [NbCl₆] octahedra. The parallel alignment of infinite ladders yields a one‐dimensional structure, with lithium ions occupying voids in a linearly aligned manner. Each ladder combines characteristic fragments from the niobium chloride structures NbCl₄, A₃Nb₂Cl₉ (A = Rb, Cs), and Nb₃Cl₈. Lithium insertion was achieved electrochemically by slow scan cyclic voltammetry in PC (1 M LiClO₄) electrolyte. 3.73 moles of lithium per formula unit could be intercalated, with a high degree of reversibility, to a composition close to Li₅Nb₆Cl₁₉ stoichiometry.     

Effect on thermal and combustion behaviors of montmorillonite intercalation nickel compounds in polypropylene/IFR system

A new montmorillonite intercalation nickel compound (MINC) was devised and synthesized. MINC was modified by cetyl trimethyl ammonium bromide to obtain organic MINC (OMINC). The results of X‐ray diffraction show that the layer spacing was expanded by nickel compound and cetyl trimethyl ammonium bromide, indicating that OMINC was prepared successfully. OMINC was further incorporated into polypropylene (PP)/intumescent flame retardant (IFR) system for preparing PP/IFR/OMINC nanocomposites via melt blending. In thermogravimetric analysis, PP/IFR/OMINC nanocomposites exhibit an enhanced thermal behavior and residue amount. Vertical burning test (UL‐94) and limited oxygen index results show that PP/IFR/OMINC nanocomposites have excellent flame retardance, i.e. the limited oxygen index value at 29.5 and UL‐94 V0 level for PP/IFR/4 wt% OMINC nanocomposites. According to cone calorimeter testing, the addition of OMINC brings an efficient reduction of flammability parameters, such as peak heat release rate, total heat release, and smoke production rate. Copyright © 2015 John Wiley & Sons, Ltd.     

苯并噻唑 盐催化合成1,4-二羰基化合物

在苯并噻唑 盐和三乙胺存在下, 醛可以作为酰基负离子的合成等价物对α,β-不饱和酮进行Michael加成, 生成相应的1,4-二羰基化合物. 文中对 盐的制备, 催化反应条件及催化反应的机理进行了研究和讨论.     

TG characterization of organically modified montmorillonite

Montmorillonite was modified with octadecyltrimethylammonium chloride, under different reaction conditions, as evidenced by TG and XRD. TG curves presented two degradation peaks (295 and 395°C). At low salt concentrations, only the 395°C-degradation appeared, which increased with reaction time to the limit of 9 g of salt/100 g of clay. The second peak presented a limit at 17/100 m/m of salt/clay ratio. XRD analysis confirmed clay organic modification as the basal distance increased, showing greater reaction time effect than the salt mass effect, and with only one d-spacing. This suggested that an intercalation complex was formed but also that octadecyltrimethylammonium was adsorbed on the external surfaces of clay particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermogravimetric analysis of calcium montmorillonite treated with hexamethylene diisocyanate

The product of the reaction between calcium montmorillonite and hexamethylene diisocyanate in acetone, catalyzed with dibutyltin dilaurate, was studied by thermogravimetry to determine the amount of polymer produced. The method developed to determine polymer content in the clay possessed excellent accuracy and precision, and produced more consistent results than traditional gravimetric methods.This research originated as a portion of the author's Master's degree research undertaken at California State Polytechnic University Pomona, and conducted at the Getty Conservation Institute (GCI). The author is indebted to the following colleagues at the GCI for providing advice and direction: Neville Agnew, Charles Selwitz, Dusan Stulik, James Druzik, David Scott and William Ginell. Consolidated adobe samples were prepared at the GCI by Richard Coffman, and by Dr. Michael Geis, department of Chemistry, Loyola University. Much valuable information and technical assistance was provided by Dr. Hans Wiedemann and Genia Paul, both of Mettler Instrument Corporation.     

Melt-processable syndiotactic polystyrene/montmorillonite nanocomposites

Monoalkyl- and dialkyl-imidazolium surfactants were used to prepare organically modified montmorillonites with markedly improved thermal stability in comparison with their alkyl-ammonium equivalents (the decomposition temperatures increased by ca. 100 °C). Such an increase in the thermal stability affords the opportunity to form syndiotactic polystyrene (s-PS)/imidazolium-montmorillonite nanocomposites even under static melt-intercalation conditions in the absence of high shear rates or solvents. Upon nanocomposite formation, s-PS exhibited an improvement in the thermal stability in comparison with neat s-PS, and the β-crystal form of s-PS became dominant. This crystallization response agrees with previous studies of s-PS/pyridinium-montmorillonite hybrids and is tentatively attributed to a heterogeneous nucleation action by the inorganic fillers. © 2003 Wiley Periodicals, Inc.* J Polym Sci Part B: Polym Phys 41: 3173–3187, 2003     

Modeling of the adsorption of organic compounds on polymeric nanofiltration membranes in solutions containing two compounds.

The adsorption of organic compounds in aqueous solution on polymeric nanofiltration membranes is studied; this process is one of the most important fouling mechanisms influencing the flux and retention behavior of nanofiltration membranes. It is shown that the adsorption of dissolved organic compounds on polymeric nanofiltration membranes is comparable to that on activated carbon. Freundlich and Langmuir isotherms are used to describe the relation between the adsorbed mass on the membrane and the equilibrium concentration of the organic compound in a single-compound solution. Based on these results, three models for the adsorption of solutions containing several compounds [i.e., the simple competitive adsorption model (SCAM), the model of Jain-Snoeyinck, and the model of Butler-Ockrent] were used to predict the adsorption behavior of an organic compound in an aqueous solution containing two compounds. The results of the three models were compared to experimental observations. It is shown that the SCAM allows a good prediction of the adsorption behavior.