Crossed Molecular Beams and Theoretical Studies of the O(3P)+1,2-Butadiene Reaction: Dominant Formation of Propene+CO and Ethylidene+Ketene Molecular Channels

Detailed understanding of the mechanism of the combustion relevant multichannel reactions of O(³P) with unsaturated hydrocarbons (UHs) requires the identification of all primary reaction products, the determination of their branching ratios and assessment of intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). This can be best achieved combining crossed-molecular-beam (CMB) experiments with universal, soft ionization, mass-spectrometric detection and time-of-flight analysis to high-level ab initio electronic structure calculations of triplet/singlet PESs and RRKM/Master Equation computations of branching ratios (BRs) including ISC. This approach has been recently demonstrated to be successful for O(³P) reactions with the simplest UHs (alkynes, alkenes, dienes) containing two or three carbon atoms. Here, we extend the combined CMB/theoretical approach to the next member in the diene series containing four C atoms, namely 1,2-butadiene (methylallene) to explore how product distributions, branching ratios and ISC vary with increasing molecular complexity going from O(³P))+propadiene to O(³P)+1,2-butadiene. In particular, we focus on the most important, dominant molecular channels, those forming propene+CO (with branching ratio ∽0.5) and ethylidene+ketene (with branching ratio ∽0.15), that lead to chain termination, to be contrasted to radical forming channels (branching ratio ∽0.35) which lead to chain propagation in combustion systems.     

可X射线显影的新型碘代聚碳酸酯的设计与合成

以丝氨醇、 4-碘苯甲酰氯和氯甲酸乙酯为原料, 通过酰胺化和分子内关环两步反应合成了一种新型的碘代环碳酸酯功能单体——4-碘-N-(2-氧代-1,3-二噁烷-5-基)苯甲酰胺(IBTMC). 以异戊醇为引发剂, 1,5,7-三叠氮双环(4.4.0)癸-5-烯(TBD)为催化剂, 使IBTMC与三亚甲基碳酸酯(TMC)进行开环共聚, 合成了一系列具有X射线不透过性的碘代聚碳酸酯材料, 并采用核磁共振氢谱( ¹H NMR)、 凝胶渗透色谱(GPC)、 差示扫描量热仪(DSC)、 热重分析(TGA)和X射线计算机断层成像系统(Micro-CT)表征了其化学结构与组成、 分子量与分子量分布、 热力学性能及X射线不透过性. 研究结果表明, 本文合成的碘代聚碳酸酯具有较窄的分子量分布、 良好的热稳定性及可调的X射线不透过性. 小鼠体内埋置实验结果表明, 碘代聚碳酸酯具备体内X射线成像的能力.     

Effect of annealing temperature on the decomposition of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ films were deposited on glass substrates by reactive sputtering of a composite silver-copper target. The deposited films were annealed in air at 100, 200 and 300 °C. The structure of the films was studied using X-ray diffraction (XRD), their surface morphology was characterised using scanning electron microscopy (SEM) and their electrical resistivity at room temperature was measured using the four point probe method. The 100 °C annealing did not modify either the film structure or the film morphology. On the other hand, Ag₂Cu₂O₃ films were partially decomposed into Ag and CuO after a 200 °C annealing. The decomposition was complete for a 300 °C annealing. The evolution of the film surface morphology as a function of the annealing temperature was discussed in connection to the evolution of the molar volume of the phases constituting the films.     

Structural and electrical characterisation of strontium zirconate proton conductor co-sputter deposited coatings

SrZr_1−x Y _x O₃ coatings were co-sputtered from metallic Zr–Y (84–16 at.%) and Sr targets in the presence of a reactive argon–oxygen gas mixture. The structural and chemical features of the film have been assessed by X-ray diffraction and scanning electron microscopy. The electrical properties have been investigated for different substrates by Complex Impedance Spectroscopy as a function of crystalline state, temperature and atmosphere. The as-deposited coatings are amorphous and crystallise after annealing at 673 K for 2 h under air. The stabilisation of the perovskite structure is a function of the nominal composition. The films are dense and present a good adhesion on different substrates. Crystallisation and mechanical stresses are detected by alternating current (AC) impedance spectroscopy. Significant ionic conductivity in the 473–823 K temperature range is evidenced in air. Two different conduction regimes in the presence of steam are attributed to a modification of the charge carrier nature. In spite of low conductivity values (σ ~10⁻⁶ S.cm⁻¹ at 881 K), the activation energies are in agreement with that of Y-doped strontium zirconate ceramics (~0.7 eV in air).     

Effect of the oxygen flow rate on the structure and the properties of Ag-Cu-O sputtered films deposited using a Ag/Cu target with eutectic composition

Ag-Cu-O films were deposited on glass substrates by reactive sputtering of a composite Ag₆₀Cu₄₀ target in various Ar-O₂ mixtures. The films were characterised by energy dispersive X-ray analysis, X-ray diffraction, UV-visible spectroscopy and using the four point probe method. The structure of the films is strongly dependent on the oxygen flow rate introduced in the deposition chamber. The variation of the oxygen flow rate allows the deposition of the following structures: Ag-Cu-(O) solid solution, nc-Ag + nc-Cu₂O, nc-Ag + nc-(Ag,Cu)₂O and finally X-ray amorphous. UV-visible reflectance measurements confirm the occurrence of metallic silver into the deposited films. The increase of the oxygen flow rate induces a continuous increase of the film oxygen concentration that can be correlated to the evolution of the film reflectance and the film electrical resistivity. Finally, the structural changes vs. the oxygen content are discussed in terms of reactivity of sputtered atoms with oxygen.     

Microstructure and properties of TiC-Fe36Ni cermet coatings by reactive plasma spraying using sucrose as carbonaceous precursor

This study is aimed to introduce an innovative precursor pyrolysis process to prepare Ti-Fe-Ni-C compound powder and to discuss and evaluate the relationship between microstructure and properties of TiC-Fe36Ni cermet coatings in-situ synthesized by reactive plasma spraying (RPS) of these compound powders. The main characteristic of the pyrolysis process is that sucrose (C12H22O11) is used as a source of carbon as well as a binder to bind reactive constituent particles. The compound powder with high bonding strength can avoid the problem that reactive constituent particles are separated during spraying. The TiC-Fe36Ni cermet coatings present typical splat-like morphology of thermally sprayed coatings and consist of two different areas: one is a composite reinforcement area where spherical fine TiC particles (100-500 nm) homogeneously distribute within the Fe36Ni matrix; the other is an area of TiC accumulation. The surface hardness of the coatings reaches about 90 ± 2 (HR15N). The maximum and average microhardness values of the coatings are 1930 HV_0.2 (Vicker Hardness) and 1640 HV_0.2, respectively. The average bonding strength of the coatings is about 62.3 MPa. The wear resistance property of the coatings is much more than that of Ni60 alloys coatings.     

Numerical computation of transient shocked chemically reactive flows

Using the ability of the method of characteristics to evaluate shock fronts in an accurate manner, a formulation is presented which incorporates the effect of rapid exothermic chemical reactions in the flow. The formulation is applied to the computation of the unsteady reactive flow field behind a cylindrial expanding blast wave propagating in a mixture of hydrogen and oxygen. Details of the computational procedure are described. Results are presented for a sample problem and compared with those for the non-reactive case to illustrate the influence of chemical reactions.     

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

Electrospray ionization mass spectrometry (ESI-MS) coupled to a microreactor is an excellent tool for the investigation of reactions in solution. Here, we report the first results of our investigations into preparatively interesting electron-transfer-initiated chain reactions in solution which proceed via radical cations as reactive intermediates. The tris(p-bromophenyl)aminium hexachloroantimonate (1)-mediated [2+2] cycloaddition of trans-anethole (2) to give 1,2-bis(4-methoxyphenyl)-3,4-dimethylcyclobutane (3) was investigated. The reaction proceeds as a radical cation chain reaction via transient intermediates 2 ⁺ and 3 ⁺ that could be detected and characterized unambiguously directly in the reacting solution by ESI-MS/MS. The identity of the intermediates was confirmed by comparison with authentic MS/MS spectra of 2 ⁺ and 3 ⁺ obtained by atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In addition, substrate and product can be monitored easily in the reacting solution by APCI-MS.Part of this work was presented at the 36th Conference of the German Society for Mass Spectrometry (DGMS).     

Photophysics and lasing correlation of pyrromethene 567 dye in crosslinked polymeric networks

The photophysical properties of the pyrromethene 567 dye incorporated in copolymers of methylmethacrylate with different acrylic and methacrylic crosslinking monomers are reported. In general, the solid matrices improve the fluorescence capacity of the dye, due to both an increase and a decrease in the radiative and non-radiative deactivation rate constants, respectively, as consequence of a more rigid environment. It is observed that there is an optimal crosslinking degree for the highest fluorescence efficiency, which depends on the nature of the crosslinking monomer. Taking into account the lasing properties for these systems, it is established a good correlation between the lasing and the fluorescence characteristics of the dye in agreement with previous conclusions obtained in liquid solutions.