Molecular aggregation of rhodamine dyes in dispersions of layered silicates: influence of dye molecular structure and silicate properties

The molecular aggregation of six rhodamine dyes (rhodamine 560, B, 3B, 19, 6G, 123) in layered silicate (saponite and fluorohectorite) dispersions was investigated by using visible (vis) spectroscopy. The dye molecular aggregation was influenced by the properties of both the silicates and the dyes themselves. The layer charge of the silicates enhanced the molecular aggregation of the hydrophilic, cationic dyes. The presence of a carboxyl acid group in the dye molecules inhibited adsorption of the dyes on the surface of fluorohectorite, a silicate with a high charge density. A lower or no adsorption could be observed by vis spectroscopy. Strong association of the dyes to the silicate surface led to remarkable changes in the dye spectra, mainly due to the molecular aggregation. Dye assemblies initially formed after mixing the dye solutions with silicate dispersions were unstable. Decomposition of the dye molecular assemblies, and the formation of new species or molecular aggregate rearrangements, were studied on the bases of time-difference spectra. The reaction pathways were specific, not only for the dyes, depending upon their molecular structure and properties, but also on the silicate substrates.     

Isomerization of cationic azobenzene derivatives in dispersions and films of layered silicates

Photoisomerization reactions of cationic azobenzene dyes in solutions, dispersions, and films of layered silicates were studied by visible (Vis) spectroscopy. The dyes isomerized reversibly from thermodynamically more stable trans-isomers to cis-isomers when irradiated with ultraviolet (UV) light. Observed trends were compared with the optical changes of the dyes that occurred as a consequence of their adsorption at the silicate surface. Small fractions of the dyes are likely to have isomerized during the adsorption process, even without the UV-light irradiation. The aggregation of the dyes was another reaction taking place at the surface of the silicates. The extent of the UV-light-induced isomerization reactions was reduced for the adsorbed dye cations. The reaction proceeded readily for a dye with monovalent cations. However, the photoisomerization was practically negligible in both dispersions and films of layered silicates for a dye with bivalent cations, whereas the isomerization proceeded in solution. This phenomenon was interpreted in terms of the attractive electrostatic forces between the substrate and the dye cations, which hindered the isomerization reaction. The layer charge of silicates affected the orientation of the dye cations as observed by X-ray diffraction (XRD) measurements. However, the choice of silicate did not significantly affect the fundamental aspects and the described basic trends of the UV-light-induced isomerization reaction.     

Spectral properties and structure of the J-aggregates of pseudoisocyanine dye in layered silicate films

Monolayer behavior of an ion pair amphiphile (IPA), hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS), with normal long-chain alcohols at the air/water interface was analyzed by the Langmuir trough technique with the Brewster angle microscope (BAM) observations, and the pronounced stability enhancement of a HTMA-DS monolayer with the presence of the alcohol additives was demonstrated. Two normal long-chain alcohols with alkyl chain lengths of C16 and C18, 1-hexadecanol (HD) and 1-octadecanol (OD), were chosen as the additives. The surface pressure-area and surface potential-area isotherms of the monolayers with BAM images of monolayer morphology implied that the addition of either HD or OD with a comparatively small head group in a double-chained HTMA-DS monolayer at the interface led to better molecular packing and attractive interaction between the molecules, showing a similar condensing effect as that observed in mixed phospholipid/cholesterol systems. Moreover, the monolayer hysteresis and relaxation curves indicated that the incorporation of the alcohols into a HTMA-DS monolayer was able to lessen the monolayer hysteresis and to enhance the monolayer stability. In comparison with OD, HD seemed more effective as an additive in stabilizing a HTMA-DS monolayer, most likely due to the relatively better molecular packing of HTMA-DS and HD molecules at the interface. It is inferred that the stability of a monolayer or vesicular bilayer structure composed of IPAs can be improved by adjusting the molecular packing/interaction with a suitable long-chain alcohol as the additive.     

Melt intercalation of polystyrene in layered silicates

We have studied the melt intercalation of polystyrene into organically modified sodium bentonite, a layered, mica-type silicate, using a variety of techniques. Wide-angle X-ray scattering experiments on polymer/silicate hybrid samples demonstrate that intercalation of polymer chains leads to an ∼25% increase in the spacing between silicate layers. The magnitude of this increase, compared with the radius of gyration of the melt polymer, implies a flattened conformation of chains in the galleries. Low voltage scanning electron microscopy reveals voids in the intercalated hybrid matrix that correspond to regions where pristine polymer was present in the physical mixture of polymer and silicate before intercalation. Differential scanning calorimetry shows that only unintercalated polymer contributes to the measured glass transition trace, so that the magnitude of the trace is diminished upon intercalation. © 1996 John Wiley & Sons, Inc.     

Interaction energy and surface reconstruction between sheets of layered silicates

Interactions between two layered silicate sheets, as found in various nanoscale materials, are investigated as a function of sheet separation using molecular dynamics simulation. The model systems are periodic in the xy plane, open in the z direction, and subjected to stepwise separation of the two silicate sheets starting at equilibrium. Computed cleavage energies are 383 mJ /m(2) for K-mica, 133 mJ /m(2) for K-montmorillonite (cation exchange capacity=91), 45 mJ /m(2) for octadecylammonium (C(18))-mica, and 40 mJ /m(2) for C(18)-montmorillonite. These values are in quantitative agreement with experimental data and aid in the molecular-level interpretation. When alkali ions are present at the interface between the silicate sheets, partitioning of the cations between the surfaces is observed at 0.25 nm separation (mica) and 0.30 nm separation (montmorillonite). Originally strong electrostatic attraction between the two silicate sheets is then reduced to 5% (mica) and 15% (montmorillonite). Weaker van der Waals interactions decay within 1.0 nm separation. The total interaction energy between sheets of alkali clay is less than 1 mJ /m(2) after 1.5 nm separation. When C(18) surfactants are present on the surfaces, the organic layer (>0.8 nm) acts as a spacer between the silicate sheets so that positively charged ammonium head groups remain essentially in the same position on the surfaces of the two sheets at any separation. As a result, electrostatic interactions are efficiently shielded and dispersive interactions account for the interfacial energy. The flexibility of the hydrocarbon chains leads to stretching, disorder, and occasional rearrangements of ammonium head groups to neighbor cavities on the silicate surface at medium separation (1.0-2.0 nm). The total interaction energy amounts to less than 1 mJ /m(2) after 3 nm separation.     

Pyrolysis study of a phosphorus-containing aliphatic-aromatic polyester and its nanocomposites with layered silicates

This paper deals with the thermal decomposition behaviour of a new fire retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing aliphatic-aromatic polyester and its nanocomposites with natural layered silicate (montmorillonite) under inert atmosphere studied by TGA-FTIR, Pyrolysis-GC/MS of volatile products and ATR-FTIR of non-volatile decomposition products. The phosphorus-containing polyester undergoes decomposition in two steps between 340 and 516 °C. The first step is associated with the release of carbon dioxide, acetaldehyde, ethene, acid-containing products (mainly benzoic acid) resulting in the formation of polyarylates followed by their decomposition in the second step with the evolution of carbon dioxide. DOPO-containing products, esters (mainly diethenyl terephthalate), carbon monoxide, acids and water are released through both stages. At the end of decomposition polyaromatic structures, diarylketones and organophosphorus esters built into the chemical structure of the char develop in the solid residue. The modification of the polyester with a layered silicate does not change the composition of the pyrolysis products, only their yield, and tended to diminish the charring of the polymer. A thermal decomposition scheme of the P-polyester is proposed and the mass spectra of some DOPO-containing products are discussed.     

Adsorption of gases on layered silicates at high pressures

Equilibrium adsorption of nitrogen, carbon dioxide, and argon was examined on the sodium and pyridinium forms of montmorillonite and on the hydrogen form of bentonite. The measurements were carried out at 303, 343, 373, and 400 K over pressure ranges of 0.1–90 MPa (Ar and N₂) and 0.1–6 MPa (CO₂). The amount of nitrogen vapor adsorbed was determined at 77 K and pressures from 0 to 0.1 MPa. The porous structure parameters of the studied samples were determined using adsorption isotherms of nitrogen, argon, and carbon dioxide vapors. At elevated temperatures and pressures >10 MPa, Ar and N₂ adsorption processes on the Na-form of montmorillonite and Ar adsorption on bentonite are activated, since the amounts of the gases adsorbed and adsorption volumes increase with temperature. No activated adsorption is observed for carbon dioxide adsorption on these adsorbents. A comparison of the excess adsorption isotherms of gases on the Py-form of montmorillonite and H-form of bentonite shows that adsorption in micropores predominates for the Py-form of montmorillonite, whereas for the Na-form of bentonite and H-form of bentonite adsorption occurs mainly in meso- and macropores.     

Hybrid nanostructures based on layered silicates and nitrogen-containing organic compounds

Organic-inorganic hybrid nanostructures were prepared by treatment of synthetic layered silicates of the montmorillonite structure with aliphatic and aromatic amines. The interaction of organic compounds with the surface of layered silicates was studied by transmission electron microscopy, IR spectroscopy, and differential scanning calorimetry.     

Spectral properties of TMPyP intercalated in thin films of layered silicates

The objective of this study was to investigate the spectral characteristics of tetracationic porphyrin dye (TMPyP), intercalated into films of three smectites. The smectites represented the specimens of high (Fluorohectorite; FHT), medium (Kunipia F montmorillonite; KF), and low layer charge (Laponite; LAP). Intercalation of TMPyP molecules was proven by XRD measurements. The molecular orientations of the dye cations were studied by means of linearly polarized ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. Both the UV-vis and the IR spectroscopy proved the anisotropic character of the films. The spectral analysis of the polarized UV-vis spectra and consequent calculations of tilting angles of the transition moments in the region of Soret band transitions were in the range of 25-35 degrees . The determined angles indicated that the molecular orientation of the dye cations was almost parallel to the surface of the silicates. Slightly higher values, determined for a FHT film, indicated either a slightly more tilted orientation of the dye cations or the change of molecular conformation after the intercalation of the dye. Quenching of TMPyP fluorescence was observed, resulting from the formation of bimolecular layer arrangements with sandwich-type assemblies of the dye molecules.     

Interaction between crystal violet and natural and organic cation-modified layered silicates

Adsorption and spectral methods are employed for complex studying the interaction of organic cations of crystal violet with layered silicates, kaolinite and hydromica, both natural and modified with a cationic surfactant, cetylpyridinium bromide, and a cationic polyelectrolyte, poly(hexamethyleneguanidine hydrochloride). It is shown that, on the surface of silicates modified with long-chain cationic surfactants, the examined sorbate is sorbed via the hydrophobic interaction of its aggregates with the modified surface. In the case of minerals modified with relatively hydrophilic poly(hexamethyleneguanidine hydrochloride), crystal violet cations are sorbed through the ion-exchange mechanism by displacing the functional groups of the modifier from the surface.     

Molecular orientation of rhodamine dyes on surfaces of layered silicates

Films of the layered silicates fluorohectorite (FH) and saponite (Sap) with various rhodamine dyes were prepared. The dyes with acidic as well as large hydrophobic groups in their molecule were not adsorbed on the surface of FH, which was interpreted in terms of high charge density on the surface of this silicate. All adsorbed dyes formed similar forms, such as isolated cations and H-type molecular aggregates, which were characterized by different spectral properties. Polarized ultraviolet-visible (UV-vis) spectroscopy was used for the characterization of the molecular orientation of dye chromophores on the silicate surface. The isolated dye cations and species, which absorbed light at the low energy part of the spectra, were only slightly tilted with respect to the plane of the silicate surface. The cations forming H-aggregates and absorbing light at low wavelengths were oriented in a nearly perpendicular fashion. The nearly perpendicular orientation was observed as a strong increase of dichroic ratio with film tilting. The orientation of the cations in H-aggregates depends partially on the structure of the dye molecule, namely, on the type of amino group (primary, secondary, or tertiary) in the dye molecule. The type of amino groups probably plays a role in the suitable orientation of dye cations for effective electrostatic interaction between the cations and the negatively charged siloxane surface. X-ray powder diffraction could not distinguish dye phases of dye monomers and molecular aggregates.     

Factors and processes influencing the reinforcing effect of layered silicates in polymer nanocomposites

The analysis of the tensile yield stress of a large number polymer/layered silicate composites showed widely differing mechanical properties. The composition dependence of yield stress can be described and evaluated quantitatively by a simple model developed earlier for particulate filled polymers. The comparison of data produced in our laboratory or taken from the literature indicated that several processes may take place during the preparation of the composites and a considerable number of factors influence composite properties. Quite a few of these are often neglected and percentage increase in modulus, strength or other properties is reported in published papers instead. The most important of such effects are changing matrix properties when a functionalized polymer is used to promote adhesion (PE, PP), modification of crystalline structure due to nucleation (PA, PP), plasticization or lubrication (PVC), decreased interaction (PA, PVC, PET, rubbers) or chemical reactions (PVC, PP, PET). Using a few simple assumptions, most of which are supported by previous experience, the extent of exfoliation can be estimated quantitatively in nanocomposites. The analysis of the tensile yield stress of more than 80 composites with various matrices indicated that the extent of exfoliation is very low in most composites; it reaches maximum 10% in the best case, which corresponds to about 10 silicate layers per stack. Although the approach has limitations and several factors were neglected during analysis, this result is in agreement with observations indicating that complete exfoliation rarely can be reached in thermoplastic/clay composites. In order to achieve larger reinforcement, silicates must be exfoliated more perfectly in the future.     

Photo-and thermoinitiated formation of J and H aggregates in amorphous dispersions of a carbocyanine dye

We revealed the possibility of formation of J and H aggregates with different structures in amorphous dispersions of 3,3′-di(γ-sulfopropyl)-4,4′,5,5′-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt prepared in ethanol-water binary solutions upon photoexcitation into the absorption band of the dye dispersion or temperature change.     

Effect of organomodified layered silicates on the properties and structure of polytetrafluoroethylene

The physicomechanical and triboengineering properties and the structures of polymer composite materials based on polytetrafluoroethylene and layered silicates are studied. The triboengineering characteristics are substantially improved by the introduction of a small amount of layered silicates (2–5 wt %). It is found that the introduction of organomodified layered silicates leads to a considerable reduction in the friction coefficient, by an order of magnitude, and causes an increase in wear resistance (2000-fold). With the use of X-ray structural analysis and scanning electron microscopy, it is shown that, during friction loading, filler particles are localized on the friction surface, thereby hampering wear of the material.     

Nanocomposites of polystyrene-b-polyisoprene copolymer with layered silicates and carbon nanotubes

Nanocomposites of polystyrene-b-polyisoprene (PS-b-PI) copolymer with layered-smectite clays (organically modified montmorillonite) and nanostructured clay-carbon nanotube hybrids were prepared. The diblock copolymer was synthesized by anionic polymerization using high-vacuum techniques and was molecularly characterized by size exclusion chromatography. Carbon nanotubes were developed on clay-supported nickel nanoparticles by the CCVD method. Nanotubes attached on the clay platelets were then chemically modified to create ester groups on their surfaces. PS-b-PI nanocomposites at various polymer to reinforcement loadings were prepared by solution intercalation. The final nanocomposites were characterized by powder X-ray diffraction, FT-IR spectroscopy, thermal analysis, and scanning electron microscopy. The experiments complemented with viscometry measurements reveal the successful incorporation of the reinforcements in the polymer mass.     

Aggregation and self-assembly of amphiphilic block copolymers in aqueous dispersions of carbon nanotubes

The self-assembly (SA) of amphiphilic block copolymers (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) was investigated in dispersions of single-walled and multiwalled carbon nanotubes (SWNT and MWNT, respectively) as a function of temperature. Differential scanning calorimetry (DSC) was used for characterization of the thermal behavior of the combined polymers-nanostructures system, and spin-probe electron paramagnetic resonance (EPR) was employed for probing the local dynamic and polarity of the polymer chains in the presence of nanostructures. It was found that SWNT and MWNT modify the temperature, enthalpy, and dynamic behavior of polymer SA. In particular, SWNT were found to increase the cooperativity of aggregating chains and dominate aggregate dynamics. MWNT reduced the cooperativity, while colloidal carbon black additives, studied for comparison, did not show similar effects. The experimental observations are consistent with the suggestion that dimensional matching between the characteristic radius of the solvated polymer chains and the dimensions of additives dominate polymer SA in the hybrid system.     

Polarized XANES spectroscopy: The K edge of layered K-rich silicates

Angle-resolved XANES spectra have been collected at the potassium K edge using polarized synchrotron radiation on several natural mica crystals. Experimental data have been interpreted on the basis of the MS theory and, within this theoretical framework, the edge of this low-Z atom is decomposed so as to produce two partial patterns giving, respectively, the full in-plane absorption spectrum and the full out-of-plane one. The method here described is appropriate to describe the X-ray dichroic behaviour of solid layered compounds and/or two-dimensionally extended structures.