Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl₂ and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used.     

Syllables as processing units in handwriting production.

This research focused on the syllable as a processing unit in handwriting. Participants wrote, in uppercase letters, words that had been visually presented. The interletter intervals provide information on the timing of motor production. In Experiment 1, French participants wrote words that shared the initial letters but had different syllable boundaries. In Experiment 2, French- and Spanish-speaking participants wrote cognates and pseudowords with a letter sequence that was always intrasyllabic in French and intersyllabic in Spanish. In Experiment 3, French-Spanish bilinguals wrote the cognates and pseudowords with the same type of sequences. In the 3 experiments, the critical interletter intervals were longer between syllables than within syllables, indicating that word syllable structure constrains motor production both in French and Spanish. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 5. CHARACTERIZATION OF THE OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGARCANE BAGASSE OIL

In the present work, the chemical characterization of the oils obtained from liquefaction of different coals with sugar cane bagasse oil and also from the liquefaction of coal with monoethanolamine are presented. Characterization of the oil samples was done with the add of spectroscopic and chromatographic techniques, including UV-vis, FTIR, NMR, preparative liquid chromatography (PLC) and high resolution gas chromatography (HRGC).     

Downhole Upgrading of Extra-heavy Crude Oil Using Hydrogen Donors and Methane Under Steam Injection Conditions

An extra-heavy crude oil underground upgrading process is described which involves the downhole addition of a hydrogen donor additive under steam injection conditions (280-315°C and residence times of at least 24-h). Laboratory experiments showed a 4° increase in the API gravity (from 9 to 12°) of the upgraded product, a two-fold reduction in the viscosity and, an approximately 8% decrease in the asphaltene content with respect to the original crude. Further increases on the temperature led to products with improved properties reaching 15°API at 315°C. It was found that the presence of the natural formation (catalysts) and methane (natural gas) is necessary to enhance the properties of the upgraded crude oil. From GC and GC-MS results a reaction pathway is proposed that involves hydrogen transfers from tetralin to the extra-heavy crude oil resulting in the formation of 1,2-dihydronaphthalene. This compound is then transformed into naphthalene, further upgrading of crude oil through hydrogen donation. The results of the experiments carried out in the presence and absence of the mineral formation and with an inert solid (SiC) strongly indicate that the former acts as a catalyst and not as a heat transfer matrix. Isotopic labeling studies (CD₄ and ¹³CH₄) give evidences that, most probably, methane is involved in the upgrading reactions.     

A matrix-based approach to properness and inversion problems for rational surfaces

We present a matrix-based approach for deciding if the parameterization of an algebraic space surface is invertible or not, and for computing the inverse of the parametrization if it exists.     

Simulation-based sequential analysis of Markov switching stochastic volatility models

We propose a simulation-based algorithm for inference in stochastic volatility models with possible regime switching in which the regime state is governed by a first-order Markov process. Using auxiliary particle filters we developed a strategy to sequentially learn about states and parameters of the model. The methodology is tested against a synthetic time series and validated with a real financial time series: the IBOVESPA stock index (São Paulo Stock Exchange).     

Simultaneous HPLC quantification of total cholesterol,tocopherols and β-carotene in Barrosã-PDO veal

A simple, rapid and sensitive procedure for the simultaneous determination of total cholesterol, tocopherols and β-carotene in meat is described. The method involves a direct saponification of the meat, a single n-hexane extraction and the analysis of the extracted compounds by normal-phase HPLC, using fluorescence (tocopherols) and UV–Vis photodiode array (cholesterol and β-carotene) detections in tandem. Rates of recovery of spiked meat samples were 93% for cholesterol, 83–86% for (α-, β- and -γ) tocopherols and 89% for β-carotene. Repeatabilities were high (CV < 6%) for all determined compounds, except for δ-tocopherol. This tocopherol, which is not usually present in meat, showed a much lower recovery percentage (73%) and repeatability (12.8%). This methodology was applied for the quantification of total cholesterol, tocopherols and β-carotene in three muscles (longissimus thoracis, longissimus lumborum and semitendinosus) of the Portuguese traditional Barrosã-PDO veal, obtained from autochthonous calves fed extensively during summer (with the least abundant green pastures) and slaughtered in early autumn (October). Barrosã-PDO veal showed median contents of total cholesterol (0.50–0.56 mg/g) and, depending on the analysed muscle, moderate to high contents of α-tocopherol (3.3–3.9 μg/g) and β-carotene (0.07–0.09 μg/g), suggesting an high sensorial and hygienic quality.     

Spouted bed drying of cork stoppers

The spouted bed is commonly used to dry granular particles as it displays some special characteristics which render it capable of performing cyclic operations, with particles that are very difficult to fluidize under a different type of bed.Information on the characteristic drying rates of cork stoppers is still very limited in the technical and scientific literature, and until now no published data was found on the spouted bed drying of cork stoppers.The characterization of the drying performance of Port wine cork stoppers was carried out in a laboratory scale spouted bed. Characteristic drying curves were determined with 29 mm × 21 mm cork stoppers under several operating conditions. Values for the effective diffusivity were obtained in the range of 1.36 × 10⁻⁹ to 4.44 × 10⁻⁹ m²/s, with the temperature dependence represented by an Arrhenius-type relationship. The activation energy obtained was 28.72 kJ/mol.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.