Thermal quenching

In order for a soHd to bum it must be volatilized, because combustion is almost exclusively a gas-phase phenomenon. In the case of a polymer, this means that decomposition must occur. The decomposition begins in the soHd phase and may continue in the Hquid (melt) and gas phases. Decomposition produces low molecular weight chemical compounds that eventually enter the gas phase. Heat from combustion causes further decomposition and volatilization and, therefore, further combustion. Thus the burning of a soHd is like a chain reaction. For a compound to function as a flame retardant it must intermpt this cycle in some way. There are several mechanistic descriptions by which flame retardants modify flammabiUty. Each flame retardant actually functions by a combination of mechanisms. For example, metal hydroxides such as Al(OH)2 decompose endothermically (thermal quenching) to give water (inert gas dilution). In addition, in cases where up to 60 wt % of Al(OH)2 may be used, such as in polyolefins, the physical dilution effect cannot be ignored. 

Thermal Quenching. Endothermic degradation of the flame retardant results in thermal quenching. The polymer surface temperature is lowered and the rate of pyrolysis is decreased. Metal hydroxides and carbonates act in this way. 

At atmospheric pressure, the conversion to trichlorosilane is limited to about 16%. The conversion of SiCl to HSiCl was found to be at equiUbrium. If contact time was greater than 45 s and the mole ratio of hydrogen to siUcon tetrachloride 1 1, then at 14 kPa (2 psi) and 550°C, the HSiCl mole fraction reached 0.7 but substantial formation of H2SiCl2 occurred (62). Enhancements in yield have been reported through preactivating the siUcon mass by removal of oxides (73) and the rapid thermal quench of the effluent gas stream (74). The reduction of siUcon tetrachloride in a plasma has also been reported (75). 

Design of explosion suppression systems is clearly complex, since the effectiveness of an explosion suppression system is dependent on a large number of parameters. One Hypothesis of suppression system design identifies a limiting combustion wave adiabatic flame temperature, below which combustion reactions are not sustained. Suppression is thus attained, provided that sufficient thermal quenching results in depression of the combustion wave temperature below this critical value. This hypothesis identifies the need to deliver greater than a critical mass of suppressant into the enveloping fireball to effect suppression (see Fig. 26-43). 

Fig. 6.3. The VIR Model of Horie considers the chemical reaction process in terms of three components void, inert, and reactants. The influence of the inerts is critical as that component causes thermal quenching of incipient reactions.

GP 11] ]R 19] The suppression of explosive homogeneous gas-phase reactions is not due simply to thermal quenching as a result of the heat losses from a micro reactor, but rather to radical quenching [9]. The micro reactor will therefore be safe even when heat losses from the reaction micro channel are reduced by design modifications. 

Relaxation of Thermally Quenched or Optically Excited High-Spin States Resulting... 

For iron(III) eomplexes, uic venues /vlh [Fe(aepa)2]BPh4 H2O and k = 6.7 x 10 s for [Fe(mim)2(salacen)]PF6 have been obtained [156, 166]. The rate constants derived from the line shape analysis of Mossbauer spectra thus vary between 2.1 x 10 and 2.3 x 10 s at room temperature, no significant difference between iron(II) and iron(III) being apparent. In addition, it is evident that the rates of spin-state conversion in solution and in the crystalline solid are almost the same. For iron(II) eomplexes, for example, the solution rates vary between /cjjl = 5 x 10 and 2 x 10 s , whereas in solid compounds values between kjjL = 6.6 x 10 and 2.3 x 10 s have been obtained. Rates resulting from the relaxation of thermally quenched spin transition systems are considerably slower, since they have been measured only over a small range of relatively low temperatures. Extrapolation of the kinetic data to room temperature is, however, of uncertain validity. 

Thermal quenching of the crosslinking reaction In an actual reactive extrusion process, the degree of crosslinking can be controlled by adjusting the residence time at elevated temperature. 

The resin contained 100.00 parts Epon 828, 80.00 parts NMA and 2.00 parts of BDMA. A part is a unit of mass. This formulation yields a resin with good mechanical performance. The formulation was cured in small test tubes that were placed in an electrically-heated, forced-air circulating oven which was controlled within 0.1°C of the set temperature. Specimens were removed with increasing time, thermally quenched and stored at -25°C. 

Oncul S, Demchenko AP (2006) The effects of thermal quenching on the excited-state intramolecular proton transfer reaction in 3-hydroxyflavones. Spectrochim Acta A Mol Biomol Spectrosc 65 179-183... 

A wide variety of process-induced defects in Si are passivated by reaction with atomic hydrogen. Examples of process steps in which electrically active defects may be introduced include reactive ion etching (RIE), sputter etching, laser annealing, ion implantation, thermal quenching and any form of irradiation with photons or particles wih energies above the threshold value for atomic displacement. In this section we will discuss the interaction of atomic hydrogen with the various defects introduced by these procedures. 

What makes this acceptor interesting is that its concentration can be varied reversibly over a wide range. Thermal quenching and annealing experiments showed that the acceptor must be due to a center that undergoes dissociation/recombination reactions. The following arguments led to... 

The ruthenium(II) polypyridyl complexes are also popular but the brightnesses do not exceed 15,000 and thermal quenching is rather significant. This property can be utilized to design temperature-sensitive probes providing that the dyes are effectively shielded from oxygen (e.g., in polyacrylonitrile beads). Despite often very high emission quantum yields the visible absorption of cyclometallated complexes of iridium(III) and platinum(II) is usually poor (e < 10,000 M-1cm-1), thus,... 

In summary, the use of fluorescence lifetime monitoring for temperature sensing at high temperatures is based on the phenomenon of thermal quenching of fluorescence, while this phenomenon is j u st the very obstacle that blocks the extending of the measurement further into higher temperatures. Therefore, fluorescence thermometry is intrinsically more effective for measurement within moderate temperature regions, due to this fundamental nature of the fluorescence emission itself. 

Flames interact with the walls of a combustor through various mechanisms, which affects flame stability and pollutant emissions. For example, thermal quenching by cold walls in internal combustion engines can cause an increase of unburned hydrocarbon emissions [1-3], as has been shown by impinging a... 

It is expected that as one increases the heat transfer coefficient in a stagnation reactor for nonextinguishable mixtures through straining, one could approach the PSR behavior regarding the role of thermal quenching in NOj, emissions. 

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