Thermal studies of charged cathode material (LixCoO2) with temperature-programmed decomposition-mass spectrometry

Thermal reactions of charged Li_xCoO₂ and electrolyte are investigated by means of temperature-programmed decomposition-mass spectrometry (TPD-MS), DSC, TGA, and XRD. The electrolyte is composed of ethylene carbonate, propylene carbonate, and dimethyl carbonate. Direct observation of gas species resulting from the reactions is beneficial in understanding the reaction mechanisms. From O₂ peaks in the TPD-MS spectra with weight loss in TGA and XRD results, it is obvious that the reduction of Li_xCoO₂ to LiCoO₂ and Co₃O₄ is triggered at 190 °C and completed at 400 °C. The initial stages of electrolyte combustion and decomposition are confirmed by H₂O and CO₂ peaks in the TPD-MS spectra along with exothermic peaks in DSC plots. The reaction of electrolyte with O₂ released from the reduction of Li_xCoO₂ begins at 240 °C; the decomposition starts at 290 °C.     

Application of multivariate statistical methods to extend the authenticity control of flavour constituents of apple juice

 The distribution of 15 aroma constituents, including the (R)- and (S)-enantiomers of ethyl 2-methylbutanoate, in 30 commercially available and laboratory prepared apple juices was evaluated by multivariate statistical methods. Principal component analysis and cluster analysis revealed ethyl 3-methylbutanoate, 3-methylbutyl acetate and (R)-ethyl 2-methylbutanoate as key components for the differentiation of apple juices. In freshly pressed and some commercial juices ethyl 3-methylbutanoate and 3-methylbutyl acetate were not present, and the (S):(R) ratio of ethyl 2-methylbutanoate was found to be >99 : 1%. Another group of commercial products was separated in which the amounts of ethyl 3-methylbutanoate and 3-methylbutyl acetate exceeded 1 μg/l and 180 μg/l, respectively, and in which the (S):(R) ratio of ethyl 2-methylbutanoate was <97 : 3%. The statistical data confirmed the high selectivity of apple fruit tissue in biosynthesizing 2-methylbutyl and 2-methylbutanoate esters, and could also be used to extend the results of enantio-multidimensional gas chromatography and other authenticity analyses. Received: 20 April 1998 / Revised version: 23 June 1998     

HS-SPME coupled to GC/MS for quality control of Juniperus communis L. berries used for gin aromatization

HS-SPME coupled to GC/MS was applied to the analysis of the volatile fraction of Juniperus communis L. berries, which are the principal ingredient used for gin aromatization. Seventy seven compounds were identified by comparison with reference compounds or tentatively identified by comparing their mass spectra and retention index with those reported in mass spectra libraries and literature, respectively. Seventy four were detected by SPME and sixty eight were detected by solvent distillation extraction (SDE). These were mainly mono- and sesquiterpenic compounds that represented more than the 80% of the gin’s volatile composition. A high percent content was due to monoterpenoids, whose analysis could be important for the assessment of sensory quality control of juniper due to their impact on gin aroma. The main monoterpenoids detected in the headspace of the juniper berries from two periods of collection were terpinen-4-ol, p-cymene, β-myrcene, γ-terpinene, α-pinene and limonene. These represented more than the 70% of the sample’s volatile fraction. The proposed SPME method required short times and the low cost of analysis and enabled to detect a number of compounds comparable with SDE or much higher than the number of compounds reported by other extraction techniques. The results suggested the suitability of this technique for the assessment of the volatile composition of juniper berries intended for gin flavouring.     

Dilute-and-shoot procedure for the determination of mineral constituents in vinegar samples by axially viewed inductively coupled plasma optical emission spectrometry (ICP OES)

Samples of commercial wine vinegar were introduced in an axially viewed inductively coupled plasma optical emission spectrometry instrument (AX-ICP OES) equipped with different sample introduction systems: a cross-flow nebulizer combined with a double-path spray chamber (CF-DP) and cone spray associated with a cyclone spray chamber (CS-CC). Samples of white and red wine vinegar were diluted with water before analysis. Higher magnesium Mg II/Mg I ratios (11 and 10 for CS-CC and CF-DP, respectively) were obtained using a nebulization gas flow rate of 0.6 l min^-1 and an applied power of 1.3 kW. The background equivalent concentrations (BEC) and signal-to-background ratio (SBR) of analytes were improved using scandium (Sc) as the internal standard. The limits of detection (LOD) and limits of quantification (LOQ) for mineral constituents were similar for both introduction systems. Best recoveries values were obtained using a plasma under robust conditions, CS-CC system and Sc as the internal standard. The concentration determined in 13 commercial samples of wine vinegars varied between 0.2 and 3.0, between 0.02 and 0.4, between 8.5 and 100.0, between 0.01 and 0.05, between 27.0 and 540.0, between 4.0 and 79.0, between 0.4 and 10.0, and between 0.01 and 2.0 for aluminium (Al), barium (Ba), calcium (Ca), copper (Cu), potassium (K), magnesium (Mg), manganese (Mn), and zinc (Zn), respectively.     

Modeling of heat and mass transfer coupling with gas-solid reaction in a sorption heat pump cooled by a two-phase closed thermosyphon

A model for the global dynamics of a sorption heat pump is presented in this work. It involves a model of a reactor where gas-solid reaction takes place coupled with a model of a two-phase closed thermosyphon cooling exchanger. Simulations of the whole discontinuous cold production process have been performed. The good agreement between experimental and simulation data shows the ability of the present model to accurately represent the dynamics of such systems. An analysis of the physical mechanisms governing the dynamics of each process stage is made. It was shown that mass limitation strongly slowed down the synthesis when the other phases of the process are mainly dependent on the thermal behavior of the transformer. This model can be used as a powerful tool for the optimization of sorption systems and for the intensification of such processes.     

An adaptive hybrid time‐stepping scheme for highly non‐linear strongly coupled problems

This paper deals with the design and implementation of an adaptive hybrid scheme for the solution of highly non‐linear, strongly coupled problems. The term ‘hybrid’ refers to a composite time stepping scheme where a controller decides whether a monolithic scheme or a fractional step (splitting) scheme is appropriate for a given time step. The criteria are based on accuracy and efficiency. The key contribution of this paper is the development of a framework for incorporating error criteria for stepsize selection and a mechanism for choosing from splitting or monolithic possibilities. The resulting framework is applied to silylation, a highly non‐linear, strongly coupled problem of solvent diffusion and reaction in deforming polymers. Numerical examples show the efficacy of our new hybrid scheme on both two‐ and three‐dimensional silylation simulations in the context of microlithography. Copyright © 2005 John Wiley & Sons, Ltd.     

Modern mass spectrometry for coatings

For the analysis of polymers soft ionization mass spectrometry, in which only molecular ions are observed, can provide the complete distribution of chains (length, composition, end-groups) in under ten minutes on microgram quantities of material. Moreover, molecular ion information of neat organic pigments or those present in crosslinked networks can also be furnished. No other analytical technique can supply these data in such a short time. The application of mass spectrometry to the characterization of materials used in today's high performance automotive coatings is presented. These include functional monomers, several acrylic copolymers, organic pigments and an epoxide prepolymer. While there are a variety of mass spectrometric techniques, in this paper we will highlight the techniques that we have found useful for the characterization of organic coating components. The selection of the mass spectrometric technique is dictated by the molecular weight of the material and to a lesser extent the chemical composition. We used potassium ionization of desorbed species (K⁺IDS) performed on a quadrupole mass spectrometer for materials under 1000 Daltons (Da). However, many of the ingredients used in current automotive finishes fall between 1000 and 10 000 Da. For these materials we used a Fourier transform mass spectrometer (FTMS) which is well suited for this mass range and boasts the highest resolution and mass accuracy available. Direct desorption/ionization using a carbon dioxide laser is our standard method of sample introduction. Recently, we coupled a gel permeation chromatograph to our FTMS using an electrospray ionization interface. This hyphenated technique offers one of the most powerful characterization methods for the coatings chemist.     

建筑双层外窗复合传热过程交叉效应的研究

应用不可逆热力学分析并实验测试了双层窗的复合传热过程 ,得出 :在不考虑日射得热的条件下 ,自然对流换热及其对辐射换热的交叉效应是传热过程的主要因素 ,说明降低窗间气体的自然对流将是提高外窗的绝热性能的主要方向之一。