Calcium Silicate Phases Explained by High-Temperature-Resistant Phosphate Probe Molecules.

In this work, high-temperature-resistant phosphate molecules are applied to characterize ultrathin (100 nm) calcium silicate (C-S) phases. These C-S phases are synthesized on silicon wafers, and the interaction of phosphates with the C-S phases is studied by means of in situ transmission Fourier transform infrared (FTIR) spectroscopy. At room temperature, the chemistry of the system is dominated by the formation of calcium phosphates (C-P). In the case of temperature rising to 1000 °C, the C-S phases are regenerated. FTIR results are analyzed on the basis of first-principles calculations and further supported by complementary time-of-flight secondary ion mass spectrometry (ToF-SIMS) experiments. This study provides a detailed and self-consistent picture of the chemical and structural properties of interfaces such as the one between the atmosphere and ultrathin C-S phases (gas/C-S) and the one between them and silicon wafers (C-S/Si bulk). The material combination of ultrathin C-S phases grown on silicon wafers might in the future have great potential in selective chemistry, catalysis, and sensing technology as well as in semiconductor manufacturing.

New dielectric sensors and sensing techniques for soil and snow moisture measurements.

Measurements of material moisture are essential in fields such as agriculture or civil engineering. Electromagnetic techniques, more precisely dielectric methods, have gained wide acceptance in the last decades. Frequency or Time Domain methods take advantage of the high dielectric permittivity of water compared to dry materials. This paper presents four new dielectric sensors for the determination of soil or snow water content. After a short introduction into the principles, both the hardware and operating mode of each sensor are described. Field test results show the advantages and potentials such as automatic measurement and profiling, state-of-ground detection or large-scale determination. From the results it follows that the presented sensors offer promising new tools for modern environmental research.

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.

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.