Curie-point pyrolysis field ionization mass spectrometry of carbohydrates: Part A: Methodology

Methodological aspects of Curie-point pyrolysis in combination with field ionization mass spectrometry for the characterization and identification of carbohydrates are reported. Some monomeric sugars and sugar derivatives have been investigated as a first step towards a basic understanding of the pyrolysis pathways of polysaccharides.Curie-point pyrolysis is performed inside the ion source of a double-focusing mass spectrometer close to the field ion emitter. The pyrolysis products are ionized in a high electric field and spectra of high mass resolution are recorded photographically. This procedure essentially avoids mass spectrometric fragmentation and yields almost exclusively molecular ions of the pyrolysates. The best experimental conditions for pyrolysis were determined by investigating the influences of pyrolysis temperature, temperature pulse length, exposure time and trace impurities on the pyrolysis products. At a temperature of 500°C and a pulse length of 4–6 s, the most significant pyrolysis fragments appear with high relative intensity. Although most of the pyrolysis products with higher volatility are pumped out of the ion source after an exposure time of 3 min, the more characteristic degradation products of lower volatility can still be registered after 10 min. The spectra of monosaccharides such as glucuronic acid, d-glucose and some of its methylated derivatives show significant differences which can be correlated structurally with the position of the substituent.     

Fracture mechanical damage modelling of thermal barrier coatings

Summary The problem of how to avoid damage of TBCs has been approached by calculating the energy release rate of two crack configurations under thermal loading. This has been done for the limiting cases of perfect and lacking heat transfer across the crack. Suitable grading of TBCs is a means of suppressing the tendency to delamination and damage by both decreasing the energy release rate G and increasing its critical value G _c . TBCs can be graded such that delamination cracks would be deflected into depth where G _c is sufficiently high to avoid crack propagation. Received 31 March 1999; accepted for publication 10 June 1999     

Electronic structure of the surface of the ionic liquid [EMIM][Tf(2)N] studied by metastable impact electron spectroscopy (MIES), UPS, and XPS

The near-surface electronic structure of the room-temperature ionic liquid (RT-IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf(2)N]) has been investigated with the combination of the electron spectroscopies metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS (HeI and HeII)), and monochromatized X-ray photoelectron spectroscopy (XPS). We find that the top of the valence band states originates from states of the cation (see also ref 1). The ultimately surface-sensitive technique MIES proves that the surface layer consists of both cations and anions. The temperature dependence of the spectra has been measured between about 160 and 610 K. Information on the glass transition and the possibility for low-temperature distillation of [EMIM][Tf(2)N] at reduced pressures is derived from the present results.     

Weathering resistance of halogen-free flame retardance in thermoplastics

The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR-FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed.     

Interaction of NaI with solid water and methanol

The interaction of NaI with amorphous solid water (ASW) and methanol (MeOH) has been investigated with metastable impact electron spectroscopy (MIES), UPS(HeI), and temperature programmed desorption (TPD). We have studied the electron emission from the ionization of the highest-lying states of H(2)O, CH(3)OH, and of 5pI. We have prepared NaI layers on ASW (MeOH) films at about 105 K and annealed them up to about 200 K. Surface segregation of iodide is observed in ASW, as predicted for NaI aqueous solutions. On the other hand, surface segregation is not observed in MeOH, again as predicted for the interaction of NaI with liquid methanol. Electronic properties (ionization potentials, optical band gaps) and water binding energies are reported and are analyzed on the basis of available DFT results for hydrated NaI clusters.     

Separation and determination of non-ionic surfactants of the nonylphenol polyglycol ether type by liquid chromatography

A normal-phase method for the separation and determination of non-ionic surfactants of the 4-nonylphenol polyglycol ether (NPEO) type by liquid chromatography is described, based on a LiChrosorb-Diol column and nonpolar linear gradient elution, with spectrophotometric detection at 275 nm. The method was applied to the determination of NPEO oligomers in the technical surfactants Arkopal N-20, N-40, N-60 and N-100 and in aqueous solutions from flotation processes. The relative standard deviations were 2.47–5.62%. The detection limits for nonylphenol polyglycol ether with 2, 4, 6, 8, 10, 13 and 15 ethoxy units were 51, 57, 64, 74, 85, 118 and 132 ng, respectively. The method can also be used for the determination of other alkylphenol polyglycol ethers. Reversed-phase LC with an octadecylsilica column was investigated and can be applied to the identification of the alkyl group present.     

Multiple crack propagation in a strip caused by thermal shock

The time-dependent stress intensities due to quenching are calculated by the boundary element method for an array of parallel and equal spaced edge cracks in a long strip. Analyzed is the sequence of crack pattern formation. The predicted patterns have essential features in common with the experimental ones. This tends to support a recently developed approach for analyzing single and multiple crack growth under thermal shock.     

Multibeam effects on fast-electron generation from two-plasmon-decay instability

Experiments with multiple laser beams have been carried out in both spherical and planar geometry to study two-plasmon-decay instability, the predominant source of suprathermal electrons in direct-drive inertial confinement fusion experiments. These electrons are observed using the hard x rays generated through electron-target interactions. The experiments show for the first time that the total overlapped intensity governs the scaling of the suprathermal-electron generation regardless of the number of overlapped beams, in contrast to conventional theories that are based on the single-beam approximation.     

Thermal mismatch strains in sidewall functionalized carbon nanotube/polystyrene nanocomposites

We present an unusual temperature dependence of thermal strains in 4-(10-hydroxy)decyl benzoate (HDB) modified SWNTPS (SWNT-single wall carbon nanotube, PS-polystyrene) nanocomposites. The strain transfer from the matrix to nanotubes in these nanocomposites, inferred from the frequency change of the Raman active tangential modes of the nanotubes, is enhanced strongly below 300 K, whereas it is vanishingly small at higher temperatures. The increased strain transfer is suggestive of reinforcement of the HDB-SWNTPS nanocomposites at low temperatures. On the other hand, the pristine SWNTs couple weakly to the PS matrix over the entire temperature range of 4.5-410 K. We argue that the strain transfer in HDB-SWNTPS is determined by the thermomechanical properties of the interface region composed of polystyrene plasticized by the tethered alkanelike modifier.