An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

Influence of anionic form on thermooxidation of TMAHP–cellulose

With the help of DTA, DTG elementary analysis of carbonized residues and ESR spectroscopy the influence of anionic form on thermooxidation of trimethylammoniumhydroxyprophyl (TMAHP)–cellulose was studied. At 300°C the percentage of carbon in carbonized residue thermolyzed in oxidative atmosphere is higher than for the sample degraded in inert atmosphere. The percentage of hydrogen decreases simultaneously. The concentration of free radicals in thermolyzed residue also increases due to the presence of oxygen. We propose that oxygen is abstracting the hydrogen atoms from polysaccharide and unpaired electrons on carbon atoms are produced. At 400°C the percentage of carbon in residues prepared at inert atmosphere is higher than for residue formed at oxidative atmosphere. Also the concentration of free radicals in thermolyzed residues obtained in inert atmosphere is greater than for those from oxidative ones. That is why suppose that at this temperature oxygen is bonded to polysaccharide residue and free radicals are terminated. From the semiquantitative DTA we can make the following sequence of samples according to their increasing thermooxidative effect: unmodified cellulose < A–HSO < A–Br^? < A–I^? < A–NO < A–H₂PO < A–CH₃COO^? < A–HCO < A–F^? < A–Cl^?1 < A–OH^p?.     

Effect of temperature on the separation of some Δ9-cis-trans isomers of methyl esters of fatty acids by open tubular gas chromatography

The influence of temperature on the gas chromatographic separation ofcis-trans isomers of the methyl esters of some monounsaturated fatty acids was studied on capillary columns coated with Apiezon L, BDS and DEGS. As far as methyl oleate and methyl elaidate are concerned, the separation is better at lower temperatures on Apiezon L (180–210 C) and at higher temperatures on polyester phases (BDS, DEGS; 150–180 C). The influence of temperature on the separation ofcis-trans isomers on the three stationary phases under study is explained by the higher values of δECL/δt forcis isomers. The variation of the equivalent carbon chain length with temperature can be used for the identification ofcis-trans isomers in natural mixtures.     

Methane generation from Miocene lacustrine coals and organic-rich sedimentary rocks containing different types of organic matter

Ten selected samples with varying types and amounts of organic matter from two Miocene lacustrine basins in northwestern Turkey were analyzed by programmed-temperature open-system pyrolysis to determine methane generation potential and reaction kinetics. Open-system pyrolysis was performed at heating rates 0.1, 0.7 and 5.0 K/min, where generated gases were measured using an on-line gas chromatograph. Frequency factors and activation energy distributions of reaction kinetics for methane generation from the investigated lacustrine coals and sedimentary rocks indicated that type of kerogen controls the sequential order of methane generation. Methane from Type-III kerogen is generated at lower temperatures, which will be followed by methane from Type-II and Type-I kerogen. Methane generation potentials in the range 14-35 mg CH₄/g TOC correlates also with type of organic matter. For Type-III kerogen up to 28% of the total hydrocarbon generation potential belongs to methane. The respective value is only 2% for a Type-I kerogen.     

Preparation and characterization of PVA/OMMT composites

In this study, polyvinyl alcohol/organically modified montmorillonite (HDA/MMT; organoclay) composite was prepared for the intercalation processes. Firstly, the rheological behavior of aqueous montmorillonite dispersions was investigated as a function of solid content. Hexadecylamine (HDA) was added to the montmorillonite dispersion (2%, w/w) in different concentrations in the range of 5 × 10^?4 – 9 × 10^?3 mmol/L. The basal spacing of the organoclay (OMMT) was studied by X‐ray diffraction. The FTIR spectra are obtained from the modified montmorillonite products, which revealed the characteristic absorbencies after treatment with HDA. HDA/MMT/PVA composite, which was produced by the reaction of 1 wt % PVA solution with organoclay complex, is characterized by the rheology, electrokinetic, XRD, FTIR, and SEM techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2315–2323, 2006     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate) as a mouse embryonic stem cells support

A series of swellable ethylene dimethacrylate‐crosslinked poly(2‐hydroxyethyl methacrylate) (PHEMA) sheets of homogeneous (nonporous) structure or with different degrees of swelling and porosities was produced by bulk polymerization in either the absence or the presence of various diluents (porogens). Calculations performed by use of the solubility parameter δ of the reaction components indicate that the solvation conditions of the polymerization system change, depending on the solvating power of the diluent, which thus controls the porosity. Pore volume also seemed to be sensitive to the presence of the linear polymer diluent. Polystyrene (PS) showed, compared with poly(methyl methacrylate) (PMMA), a higher precipitating ability to form porous PHEMA sheets with an increased pore size because of its higher noncompatibility with newly formed crosslinked PHEMA. Given that PHEMA hydrogel is well known for its biocompatibility, it was used here as a potential carrier of cells in transplantation therapies. Attachment and growth of mouse embryonic stem (ES) cells on gelatin‐coated transparent PHEMA hydrogel substrates were examined. Two days after plating, survival and morphology of ES cells were largely similar on both PHEMA hydrogel sheets and in petri dishes as controls. This suggests that PHEMA hydrogels are likely candidates for application in transplantation therapies involving ES cells. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 425–432, 2003     

Relationship between gliadin peptide structure and their effect on the fetal chick duodenum

Summary The tendency to form a-turn in-gliadin was estimated using the B-cell determinant prediction program based on the Chou and Fasman probability of-turn formation. Six sequences possessing a high probability of-turn formation were found. A statistically high agreement was found between these six sequences and three areas in-gliadin with the occurrence of Pro-Ser-Gln-Gln sequence which has recently been considered responsible for toxicity in coeliac disease. By means of solid-phase synthesis seven peptides were obtained covering the above-mentioned regions. Their toxicity was tested using the fetal chick duodenum. The results support the suggestion that peptides containing the sequences Pro-Ser-Gln-Gln and Gln-Gln-Gln-Pro may be involved in the pathogenesis of coeliac disease.

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Beziehung zwischen der Gliadin-Peptid-Struktur und ihr Einfluß auf den fetalen Kückendarm

Zusammenfassung Die Tendenz zur Bildung einer-Umwandlung im-Gliadin wurde bei Anwendung eines mathematischen Programms zur Vorhersage von B-Zelldeterminanten bestimmt, welches auf der Wahrscheinlichkeit der-Umwandlung nach Chou und Fasman basiert. Es wurden 6 Sequenzen gefunden, die eine hohe Wahrscheinlichkeit für die Bildung von-Umwandlungen aufwiesen. Zwischen diesen 6 Sequenzen und 3 Regionen im-Gliadin mit der Sequenz Pro-Ser-Gln-Gln, die kürzlich als verantwortlich für die Toxizität bei Cöliakie angesehen wurden, konnte eine statistisch gesicherte Beziehung gefunden werden. Mittels Festphasensynthese wurden 7 Peptide erhalten, die die oben genannten Regionen überdeckten. Ihre Toxizität wurde im fetalen Kückendarm getestet. Die Ergebnisse weisen darauf hin, daß Peptide, welche die Sequenz Pro-Ser-Gln-Gln und Gln-Gln-Gln-Pro enthalten, an der Pathogenese der Cöliakie beteiligt sein könnten.

     

Microstructure and physical properties of transparent thoria-yttria ceramics

The investigation of microstructure, some electrical and optical parameters of transparent ThO₂-15 mol % yo_1.5 ceramics has shown: (a) a very low porosity, close to zero; (b) a higher electrical conductivity than is usual for ThO₂ ceramics of the same composition, with the activation energy 1.12 eV; (c) a relative permittivity _r 33 under the given conditions; (d) confirmation of a single-phase fluorite-type cubic structure by means of Raman and infrared spectra.     

Design of Lu2O3-reinforced Cf/SiC-ZrB2-ZrC ultra-high temperature ceramic matrix composites: Wetting and interfacial reactivity by ZrSi2 based alloys

The wettability and infiltration of molten ZrSi₂ and ZrSi₂-Lu₂O₃ alloys into C_f/SiC and B₄C-infiltrated C_f/SiC composites were investigated to understand the interfacial interactions that occur during the development of C_f/SiC-ZrC and C_f/SiC-ZrB₂-ZrC-Lu₂O₃ materials. A significant evaporation of Si from the liquid affected the wetting behaviour of the alloy when tested in a vacuum at 1670 °C. The better wetting and spreading of the alloy over the surface was observed for the composites with lower overall porosity (12 %). On the other hand, the formation of an outer dense layer, followed up by the uniform infiltrated region up to ～ 1 mm was observed for the C_f/SiC with higher porosity (21 %). The infiltrated alloy reacted with SiC matrix to form ZrC or with B₄C-infiltrated SiC matrix to form ZrB₂-ZrC-SiC. The Lu₂O₃ particles were not wetted by the melt, and were pushed away of the reaction zone by the solidification front.