Investigation of the effect of surface phosphate ester dispersant on viscosity by coarse-grain modeling of BaTiO slurry

To understand the role of phosphate ester dispersant, we investigated the rheology of a BaTiO slurry. For the model case, a coarse-grain molecular dynamics (CGMD) simulation was performed with the butyral polymer didodecyl hydrogen phosphate (DHP) in the toluene/ethanol solvent. By systematically analyzing the effect of DHP from an atomic-scale first principle and from all-atom MD to microscale CGMD simulation, we investigated how the adsorption of a DHP dispersant on a BaTiO surface affects the microstructure rheology of a BaTiO slurry. The first-principle and all-atom MD simulation suggests that DHP molecules prefer to locate near the BaTiO surface. CGMD simulation shows a reduction in viscosity with an increase in dispersants, suggesting that the dispersant population near the BaTiO surface plays a key role in controlling the rheology of the BaTiO slurry. In this study, we propose an approach for understanding the BaTiO slurry with molecular-level simulations, which would be a useful tool for efficient optimization of slurry preparation.     

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation

The conformational distribution change of amorphous poly(lactic acid) (PLA) induced by deformation has been studied using Raman spectroscopy. Spectroscopic features associated with the rotational isomeric states (ttt, ttg′, tg′t, tg′g′) have been established experimentally and supported by normal coordinate analysis. Deformation induced a significant increase in the most favorable tg′t conformation. Based on the relative intensities of Raman-active skeletal modes, a quantitative method has been developed that can be used to elucidate structural changes in a variety of deformed polymer samples. For biaxially oriented PLA films, the overall tg′t conformation increased from the 76% in undeformed sample to a value as high as 92%. The change in conformational distribution in the amorphous phase follows a different trend (76-88%) as compared to the increase in sample crystallinity (0-43%). A large change in amorphous chain conformation occurred at relatively low draw ratios. In contrast, the large change in the degree of crystallinity occurred at higher draw ratios.     

酸、碱及盐对胶乳法氯化天然橡胶热稳定性的影响

采用热老化实验结合紫外光谱分析和热分析，分析了酸、碱及盐对胶乳法氯化天然橡胶(CNR)热稳定性的影响，并讨论了酸、碱及盐对CNR热降解的影响机理。研究结果表明：胶乳法CNR产品中含有酸、碱、盐时，对CNR的结构有不利的影响，其影响随含量增高而增大，其中又以碱对结构的不利影响最大。因此，在胶乳法生产CNR的生产工艺中，最后的酸碱中和、洗涤2道工序必须严格控制工艺条件，保证半成品的pH值和含盐量达到标准。     

Effect of hydrocarbons precursors on the formation of carbon nanotubes in chemical vapor deposition

High-temperature decomposition of hydrocarbons may lead to the formation of carbon deposits. However in our present studies, we found that the morphology of carbon deposits over MgO supported Fe catalyst during chemical vapor deposition (CVD) process was closely related to the thermodynamic properties and chemical structures of hydrocarbon precursors. Six kinds of hydrocarbons (methane, hexane, cyclohexane, benzene, naphthalene and anthracene) were used as carbon precursors in this study. Methane which has a pretty simple composition and is more chemically stable was favorable for the formation of high-purity single walled carbon nanotubes (SWNTs). For high-molecular weight hydrocarbons, it was found that the chemical structures rather than thermodynamic properties of carbon precursors would play an important role in nanotube formation. Specifically, the CVD processes of aromatic molecules such as benzene, naphthalene and anthracene inclined to the growth of SWNTs. While the cases of aliphatic and cyclic hydrocarbon molecules seemed a little more complicated. Based on different pyrolytic behaviors of carbon precursors and formation mechanism of SWNTs and multi-walled carbon nanotubes (MWNTs), a possible explanation of the difference in CVD products was also proposed.     

Mandibular gland secretions of the male beewolvesPhilanthus crabroniformis,P. barbatus,andP. pulcher (Hymenoptera: Sphecidae)

The composition of the territorial marking pheromones from mandibular glands of males of the beewolvesPhilanthus crabroniformis, P. barbatus, andP. pulcher have been determined. The structures of the components were elucidated by gas chromatography-mass spectrometry and gas chromatography-Fourier transform infrared spectroscopy. The major compound ofP. crabroniformis is isopropyl tetradecanoate, with somewhat lesser amounts of 2-tridecanone, 3-methyl-3-butenyl tetradecanoate, and 928 (Z)(E)-11-eicosen-1-ol. The major compounds ofP. barbatus are ethyl tetradecanoate and hexadecanal, which are present in approximately a 6040 ratio. These two compounds comprise over 95% of the neutral lipids. Also present in lesser amounts are ethyl dodecanoate, tetradecanal, hexadecan-1-ol, a ^x -octadecen-1-ol, and octadecan-1-ol. The major compounds ofP. pulcher are ethyl (Z)-7-hexadecenoate and geranylgeraniol acetate, which comprise nearly 90% of the neutral lipid fraction, with smaller amounts of tetradecanal, pentadecanal, and ethyl hexadecanoate; trace amounts of ^x hexadecenal, hexadecanal, and octadecanal are also present.     

Reaction pathway of benzonitrile formation during toluene ammoxidation on vanadium phosphate catalysts

The reaction pathway of the ammoxidation of toluene on (VO)₂P₂O₇ used as catalyst and the interaction of potential intermediates with the pyrophosphate were studied by spectroscopic techniques (FTIR, EPR), temperature-programmed chemisorptions/ reactions (TPD, TPRS) and transient studies such as the temporal analysis of products (TAP) technique. NH₃ is chemisorbed on the catalyst surface, forming three different species, i.e., NH ₄ ⁺ ions located on BrØnsted sites, coordinatively bound NH₃ on Lewis sites and NH ₂ ^– groups, presumably P-NH₂. Toluene that is probably adsorbed on Lewis sites reacts in a first step to a benzyl radical. A subsequent partial oxidation by interaction of V^IV=O groups generates a V...O=CH-C₆H₅ surface structure. This benzaldehyde-like surface species reacts with adsorbed NH₃ according to a Langmuir-Hinshelwood mechanism. TAP experiments on ammonium-containing vanadium phosphates revealed that NH ₄ ⁺ ions could act as potential N-insertion species. No formation of benzylamine as well as the generation of V=NH surface groups as possible intermediates or N-insertion sites were observed.     

Time-of-flight studies on catalytic model reactions

Time-of-flight spectroscopy (TOF) and REMPI-TOF (resonance enhanced multi-photon ionization-TOF) were applied to measure the angular and translational energy distribution, as well as the internal state resolved energy distribution of desorption and reaction products on some model systems. Desorption of hydrogen and deuterium from clean and modified Pd(111) surfaces was studied, where the palladium sample was part of a permeation source. Water formation by reaction of oxygen with hydrogen on palladium was investigated by using different types of hydrogen supply: molecular H₂ exposure and atomic H exposure from the gas phase, as well as H exposure by permeating hydrogen. Vanadium oxide nanostructures on Pd(111) were prepared and the influence on D₂ desorption and D₂O production was investigated with the permeation technique. Additionally, deuterium desorption from sulfur and oxygen covered V(111) and V(100) surfaces was studied by TOF and REMPI-TOF spectroscopy. From the TOF spectra information concerning the reaction and desorption dynamics (activation barriers) could be gained.     

Carbon-encapsulated Fe nanoparticles from detonation-induced pyrolysis of ferrocene

Carbon-encapsulated Fe nanoparticles with size between 5 and 20 nm were synthesized via a picric acid-detonation-induced pyrolysis of ferrocene, which is characterized by a self-heating and extremely fast process. The nanoparticles exhibit well-constructed core-shell structures, with bcc-Fe cores and graphitic shells. The graphitic shells can protect effectively the cores against the attack of HNO₃ solution. The formation of the core-shell nanoparticles can be selectively controlled by adjusting the composition of the picric acid-ferrocene mixture, which determines C/Fe atomic ratio of the reaction system. The core-shell nanoparticles are preferably formed at low C/Fe atomic ratios, while tubular structures are formed at high C/Fe ratio. The possible pathway for the carbon-encapsulated Fe nanoparticles formation is discussed briefly.     

Effect of carbon fiber surface functional groups on the mechanical properties of carbon-carbon composites with HTT

The present investigation describes the quantitative measurement of surface functional groups present on commercially available different PAN based carbon fibers, their effect on the development of interface with resol-type phenol formaldehyde resin matrix and its effect on the physico-mechanical properties of carbon-carbon composites at various stages of heat treatment. An ESCA study of the carbon fibers has revealed that high strength (ST-3) carbon fibers possess almost 10% reactive functional groups as compared to 5.5 and 4.5% in case of intermediate modulus (IM-500) and high modulus (HM-45) carbon fibers, respectively. As a result, ST-3 carbon fibers are in a position to make strong interactions with phenolic resin matrix and HM-45 carbon fibers make weak interactions, while IM-500 carbon fibers make intermediate interactions. This observation is also confirmed from the pyrolysis data (volume shrinkage) of the composites. Bulk density and kerosene density more or less increase in all the composites with heat treatment up to 2600 °C. It is further observed that bulk density is minimum and kerosene density is maximum upon heat treatment at 2600 °C in case of ST-3 based composites compared to HM-45 and IM-500 composites. It has been found for the first time that the deflection temperature (temperature at which the properties of the material start to decrease or increase) of flexural strength as well as interlaminar shear strength is different for the three composites (A, B and C) and is determined by the severity of interactions established at the polymer stage. Above this temperature, flexural strength and interlaminar shear strength increase in all the composites up to 2600 °C. The maximum value of flexural strength at 2600 °C is obtained for HM-45 composites and that of ILSS for ST-3 composites.