Simultaneous thermal analysis of cationic, nonionic and anionic polyacrylamide.

Polyacrylamide (PAM) and its derivatives are the most commercially available water-soluble polymers and are frequently used for the production of clay-polymer composites. The characterization of their thermal behavior and decomposition was carried out mainly under reduced conditions by using N2, He or Ar gas flow. The object of this study was to investigate the thermal decomposition of cationic (PAMS,τ40Cl), nonionic (PAM°S), and anionic (NaPAMS,τ40) polyacrylamide under synthetic air (SynA) in detail using a thermogravimetry/differential scanning calorimetry (TG/DSC) system connected to a quadrupole mass spectrometer (MS). MS data indicated the release of NH3, CH4 and NO together with H2O, CO2 and NO2 during decomposition. The gas release differed between the three polymers. Stoichiometric calculations showed that PAMS,τ40Cl and PAM°S decomposed completely, while NaPAMS,τ40 decomposed only partially and the Na present for charge balancing remained in the form of Na2O. The thermal decomposition of PAMS,τ40Cl, PAM°S and NaPAMS,τ40 under SynA occurred via pyrolysis and oxidation reactions.

Impact of Intrinsic Structural Properties on the Hydration of 2:1 Layer Silicates.

Several 2:1 layer silicates comprising di- and trioctahedral smectites of different layer charge between 0.2 and 0.4 per formula unit and a trioctahedral vermiculite were studied by an in situ method that allowed Fourier transform infrared spectroscopy (FTIR) spectra and water vapor sorption isotherms to be obtained simultaneously. The particle size and shape of the selected materials were determined using X-ray diffraction and gas adsorption analyses, which provided an estimate of the particle size with resulting edge site proportion. The aim of this study was to elucidate the hydration mechanism in 2:1 layer silicates during desorption and adsorption of water vapor. Domains in the desorption and adsorption of water vapor of the smectite samples with a slightly increasing slope were explained by a heterogeneous layer charge distribution, which enables the coexistence of different hydration states even under controlled conditions. Whereas hysteresis was observed over the entire isothermal range of the smectites, the isotherm of the vermiculite sample only showed hysteresis in the transition from the monohydrated state (1W) to the bihydrated state (2W). We also revealed that hysteresis is a function of the layer charge distribution, the achieved water content, and the particle size with resulting edge site contribution. Increasing the edge site proportions led to an increased hysteresis. The findings from the experimental FTIR/gravimetric analysis showed that the transition from 2W to 1W and backward is visible using infrared spectroscopy. The shifting of δ(H-O-H) was influenced by the layer charge and octahedral substitutions. As a final point, we use water as a sensor molecule to describe the OH groups of the octahedral sheet and show that the observed shifts result from a change in the tilting angle. Our experimental results were supported by ab initio thermodynamic simulations that revealed the different shifting behavior of δ(H-O-H) and δ(M x+-OH-N y+) related to the differences in surface charge density and octahedral compositions.

Microscopic structure and properties of discrete water layer in Na-exchanged montmorillonite.

In this work, we focus on the atomic structure of the water interlayer of Na-exchanged montmorillonite. For two different surface charge densities, namely -0.086 and -0.172 C/m(2), the adsorption process in the presence of water is described by first principles calculations. We describe the interactions and forces for every water molecule entering the interlayer during the swelling process. In particular, the dielectric permittivity of the water interlayer is calculated. Finally, we confirm our results performing ab initio thermodynamics calculations leading to a wide range of realistic experimental scenarios.

Low-frequency dielectric properties of three bentonites at different adsorbed water states.

Three bentonites of varying smectite content were investigated by dielectric spectroscopy in the frequency range 10(-4) to 10(6) Hz after storage at well-defined humidities. The identification of relaxation processes from complex permittivity measurements was difficult, since conductivity effects were superimposed on the underlying relaxations. Relaxation peaks revealed by the dissipation factor indicated the occurrence of interfacial processes between 10(2) and 10(6) Hz. The intensity of the polarization of the electrochemical double-layer at the clay-water interface was promoted by increasing water content and was shifted to higher frequencies the higher the water content in the bentonites. Below ~1 Hz, electrode polarization (EP) was shown to be a participating process with capacitance values ranging from 0.6*10(-3) to 7.3*10(-3)F due to the accumulated charges. An equivalent circuit model was introduced that successfully described the low-frequency dielectric behavior of bentonites at low moisture levels. An included series R-CPE connection was used to describe the double-layer relaxation. At water contents up to 17%, the bulk resistivity was mainly influenced by smectite content and cation exchange capacity, whereas at water contents of ≥19%, interlayer occupation and hydration state became more important.

Correlation between the extent of catalytic activity and charge density of montmorillonites.

The clay mineral montmorillonite is a member of the phyllosilicate group of minerals, which has been detected on martian soil. Montmorillonite catalyzes the condensation of activated monomers to form RNA-like oligomers. Extent of catalysis, that is, the yield of oligomers, and the length of the longest oligomer formed in these reactions widely varies with the source of montmorillonite (i.e., the locality where the mineral is mined). This study was undertaken to establish whether there exists a correlation between the extent of catalytic property and the charge density of montmorillonites. Charge density was determined by saturating the montmorillonites with alkyl ammonium cations that contained increasing lengths of alkyl chains, [CH3-(CH2)(n)-NH3](+), where n = 3-16 and 18, and then measuring d(001), interlayer spacing of the resulting montmorillonite-alkyl ammonium-montmorillonite complex by X-ray diffractometry (XRD). Results demonstrate that catalytic activity of montmorillonites with lower charge density is superior to that of higher charge density montmorillonite. They produce longer oligomers that contain 9 to 10 monomer units, while montmorillonite with high charge density catalyzes the formation of oligomers that contain only 4 monomer units. The charge density of montmorillonites can also be calculated from the chemical composition if elemental analysis data of the pure mineral are available. In the next mission to Mars, CheMin (Chemistry and Mineralogy), a combined X-ray diffraction/X-ray fluorescence instrument, will provide information on the mineralogical and elemental analysis of the samples. Possible significance of these results for planning the future missions to Mars for the search of organic compounds and extinct or extant life is discussed.