Thermal Degradation Processes in Poly(xylylene sulfides) Investigated by Comparative Direct Pyrolysis MS and Flash Pyrolysis GC/MS Experiments

The thermal degradation processes of two sulfur polymers, poly(xylylene sulfide) (PXM) and poly(xylylene disulfide) (PXD), were investigated in parallel by direct pyrolysis mass spectrometry (DPMS) and flash pyrolysis GC/MS (Py-GC/MS). Thermogravimetric data showed that these polymers decompose with two separate steps in the temperature ranges of 250-280 and 600-650 degrees C, leaving a high amount of residue (about 50% at 800 degrees C). The pyrolysis products detected by DPMS in the first degradation step of PXM and PXD were terminated by three types of end groups, -CH3, -CH2SH, and -CH=S, originating from thermal cleavage reactions involving a series of homolytic chain scissions followed by hydrogen transfer reactions, generating several oligomers containing some intact xylylene sulfide repeating units. The presence of pyrolysis compounds containing some stilbene-like units in the first degradation step has also been observed. Their formation has been accounted for with a parallel cleavage involving the elimination of H2S from the PXM main chains. These unsaturated units can undergo cross-linking at higher temperatures, producing the high amount of char residue observed. The thermal degradation compounds detected by DPMS in the second decomposition step at about 600-650 degrees C were constituted of condensed aromatic molecules containing dihydrofenanthrene and fenanthrene units. These compounds might be generated from the polymer chains containing stilbene units, by isomerization and dehydrogenation reactions. The pyrolysis products obtained in the Py-GC/MS of PXM and PXD at 610 degrees C are almost identical. The relative abundance in the pyrolysate and the spectral properties of the main pyrolysis products were found to be in generally good agreement with those obtained by DPMS. Polycyclic aromatic hydrocarbons (PAHs) were also detected by Py-GC/MS but in minor amounts with respect to DPMS. This apparent discrepancy was due to the simultaneous detection of PAHs together with all pyrolysis products in the Py-GC/MS, whereas in DPMS they were detected in the second thermal degradation step without the greatest part of pyrolysis compounds generated in the first degradation step. The results obtained by DPMS and PSI-GC/MS experiments showed complementary data for the degradation of PXM and PXD and, therefore, allowed the unequivocal formulation of the thermal degradation mechanism for these sulfur-containing polymers.

Flow of metal into the flash gap in the last stages of a plane-strain closed-die forging operation

In closed-die forging the flash geometry should be such as to ensure that the cavity is completely filled just as the two dies come into contact at the parting plane. If metal is caused to extrude through the flash gap as the dies approach the point of contact — a practice generally resorted to as a means of ensuring complete filling — dies are unnecessarily stressed in a high-stress regime (as the flash is quite thin and possibly cooled by then), which reduces the die life and unnecessarily increases the energy requirement of the operation. It is therefore necessary to carefully determine the dimensions of the flash land and flash thickness — the two parameters, apart from friction at the land, which control the lateral flow. The dimensions should be such that the flow into the longitudinal cavity is controlled throughout the operation, ensuring complete filling just as the dies touch at the parting plane. The design of the flash must be related to the shape and size of the forging cavity as the control of flow has to be exercised throughout the operation: it is possible to do this if the mechanics of how the lateral extrusion into the flash takes place is understood for specific cavity shapes and sizes. The work reported here is part of an ongoing programme investigating flow in closed-die forging. A simple closed shape (no longitudinal flow) which may correspond to the last stages of a real forging operation is analysed using the stress equilibrium approach. Metal from the cavity (flange) flows into the flash by shearing in the cavity in one of the three modes considered here: for a given cavity the mode with the least energy requirement is assumed to be the most realistic. On this basis a map has been developed which, given the depth and width of the cavity as well as the flash thickness, will tell the designer of the most likely mode (of the three modes considered) in which metal in the cavity will shear and then flow into the flash gap. The results of limited set of experiments, reported herein, validate this method of selecting the optimum model of flow into the flash gap.

A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Laser flash photolysis study of triplets of cyclobutanethiones

Five cyclobutanethiones with different chromophores at the 3-position were examined for triplet state behaviour in benzene using laser excitation into their low lying nπ*1 band systems. A weak transient absorption attributable to the triplet state is observed in all these cases. Results concerning triplet lifetimes, intersystem crossing yields (S1 → T1), self-quenching kinetics and kinetics of energy transfer to all-trans-1,6-diphenyl-1,3,5-hexatriene and oxygen and quenching by di-t-butyl nitroxide (DTBN) are presented. Intersystem crossing yields estimated with reference to p,p′-dimethoxythiobenzophenone are roughly unity in all five cases. Self-quenching rates are found to be less than diffusion limited and this is attributed to steric crowding at the α positions (dimethyl group). The rates of oxygen and DTBN quenching compare well with those reported for several other thiones in the literature. No transients other than the triplet were detected in the above cyclobutane-thiones.

Development of a computer code to predict cooling of die and billet in forging

A hot billet in contact with relatively cold dies undergoes rapid cooling in the forging operation. This may give rise to unfilled cavities, poor surface finish and stalling of the press. A knowledge of billet-die temperatures as a function of time is therefore essential for process design. A computer code using finite difference method is written to estimate such temperature histories and validated by comparing the predicted cooling of an integral die-billet configuration with that obtained experimentally.

WinBUGS code to run a network meta-analysis

WinBUGS code and data to reproduce our network meta-analysis from "Control strategies to prevent total hip replacement-related infections: a systematic review and mixed treatment comparison" published in BMJ Open.

Triplet-state Photophysics and Transient Photochemistry of Cyclic Enethiones A Laser Flash Photolysis Study

The triplets of four cyclic enethiones, including thiocoumarin, have been investigated by nanosecond laser flash photolysis. Data are presented for transient spectra and kinetics associated with triplets, quantum yields of intersystem crossing and singlet oxygen photosensitization. The quenching of the thiocoumarin triplet (A:, = 485 nm, E:,, = 8.8 x lo3 dm3 mol-' cm-'in benzene) by several olefins, amines and hydrogen donors occurs with rate constants of 107-5 x lo9 dm3 mol-' s-'; the lower limits of quantum yields ( c#+~) for the related photoreactions, estimated from ground-state depletion, are generally small (0.0-0.1 1 in benzene, except for good hydrogen donors, namely, p-methoxythiophenol and tri-n-butylstannane) . The radical anion of thiocoumarin (A,,, = 405-435 nm) is formed in two stages upon triplet quenching by triethylamine in acetonitrile; the fast component is the result of direct electron transfer to the triplet and the slower component is assigned to secondary photoreduction of the thione ground state by the a-aminoalkyl radical derived from the triethylamine radical-cation.

Tietokannan hallintajärjestelmän optimointi flash-muistia varten

Viime aikoina yleistyneet flash-muistiin perustuvat tallennusvälineet ovat monessa suhteessa kiintolevyä parempia. Flash-muistissa on kuitenkin useita erityispiirteitä, jotka vaikeuttavat sen käyttöönottoa tietokantajärjestelmässä. Flash-muistissa kirjoittaminen on hitaampaa kuin lukeminen. Erityisesti hajanaisten sivujen päivittäminen on hidasta. Hajaluku flash-muistista on huomattavasti nopeampaa kuin kiintolevyltä. Näiden erityispiirteiden vuoksi tietokannan hallintajärjestelmä on optimoitava erikseen flash-muistia varten. Tässä optimoinnissa lähes kaikki tietokannan hallintajärjestelmän osa-alueet on toteutettava uudelleen flash-muistin näkökulmasta. Flash-muistin nopean hajaluvun ansiosta relaatioiden tiedot voidaan sijoitella flash-muistiin vapaammin kuin kiintolevylle. Yleisin tietokannoissa käytetty hakemistorakenne B+-puu ei toimi tehokkaasti flash-muistissa hajapäivitysten suuren määrän vuoksi. Flashmuistia varten on kehitetty useita B+-puun muunnelmia, joissa hajapäivitysten määrää on onnistuttu vähentämään. Puskurin hallintaa voidaan optimoida flash-muistia varten vähentämällä hitaiden kirjoitusten määrää nopeiden lukujen määrän kustannuksella sekä muuttamalla hitaita hajakirjoituksia nopeammiksi peräkkäisten sivujen kirjoituksiksi. B.3 (hardware, memory structures) H.2.2 (database management, physical design)

A computer code for enclosed natural convection in the boundary layer regime

A computer code is developed for the numerical prediction of natural convection in rectangular two-dimensional cavities at high Rayleigh numbers. The governing equations are retained in the primitive variable form. The numerical method is based on finite differences and an ADI scheme. Convective terms may be approximated with either central or hybrid differencing for greater stability. A non-uniform grid distribution is possible for greater efficiency. The pressure is dealt with via a SIMPLE type algorithm and the use of a fast elliptic solver for the solenoidal velocity correction field significantly reduces computing times. Preliminary results indicate that the code is reasonably accurate, robust and fast compared with existing benchmarks and finite difference based codes, particularly at high Rayleigh numbers. Extension to three-dimensional problems and turbulence studies in similar geometries is readily possible and indicated.

Assessment of code bias variations of BDS triple-frequency signals and their impacts on ambiguity resolution for long baselines

Carrier phase ambiguity resolution over long baselines is challenging in BDS data processing. This is partially due to the variations of the hardware biases in BDS code signals and its dependence on elevation angles. We present an assessment of satellite-induced code bias variations in BDS triple-frequency signals and the ambiguity resolutions procedures involving both geometry-free and geometry-based models. First, since the elevation of a GEO satellite remains unchanged, we propose to model the single-differenced fractional cycle bias with widespread ground stations. Second, the effects of code bias variations induced by GEO, IGSO and MEO satellites on ambiguity resolution of extra-wide-lane, wide-lane and narrow-lane combinations are analyzed. Third, together with the IGSO and MEO code bias variations models, the effects of code bias variations on ambiguity resolution are examined using 30-day data collected over the baselines ranging from 500 to 2600 km in 2014. The results suggest that although the effect of code bias variations on the extra-wide-lane integer solution is almost ignorable due to its long wavelength, the wide-lane integer solutions are rather sensitive to the code bias variations. Wide-lane ambiguity resolution success rates are evidently improved when code bias variations are corrected. However, the improvement of narrow-lane ambiguity resolution is not obvious since it is based on geometry-based model and there is only an indirect impact on the narrow-lane ambiguity solutions.

'Wet N2O oxidation' process and interface state density characterization of nanoscale nitrided SiO2 for flash memory application

In this paper we first present the 'wet N2O' furnace oxidation process to grow nitrided tunnel oxides in the thickness range 6 to 8 nm on silicon at a temperature of 800 degrees C. Electrical characteristics of MOS capacitors and MOSFETs fabricated using this oxide as gate oxide have been evaluated and the superior features of this oxide are ascertained The frequency response of the interface states, before and after subjecting the MOSFET gate oxide to constant current stress, is studied using a simple analytical model developed in this work.

A rate-one full-diversity low-complexity space-time-frequency block code (STFBC) for 4-Tx MIMO-OFDM

It is known that by employing space-time-frequency codes (STFCs) to frequency selective MIMO-OFDM systems, all the three diversity viz spatial, temporal and multipath can be exploited. There exists space-time-frequency block codes (STFBCs) designed using orthogonal designs with constellation precoder to get full diversity (Z.Liu, Y.Xin and G.Giannakis IEEE Trans. Signal Processing, Oct. 2002). Since orthogonal designs of rate one exists only for two transmit antennas, for more than two transmit antennas STFBCs of rate-one and full-diversity cannot be constructed using orthogonal designs. This paper presents a STFBC scheme of rate one for four transmit antennas designed using quasi-orthogonal designs along with co-ordinate interleaved orthogonal designs (Zafar Ali Khan and B. Sundar Rajan Proc: ISIT 2002). Conditions on the signal sets that give full-diversity are identified. Simulation results are presented to show the superiority of our codes over the existing ones.