Condensed phase composition, oxygen

Vapor pressures and vapor compositions in equilibrium with a hypostoichiometric plutonium dioxide condensed phase have been calculated for the temperature range 1500 I H 4000 K. Thermodynamic functions for the condensed phase and for each of the gaseous species were combined with an oxygen-potential model, which we extended from the solid into the liquid region to obtain the partial pressures of O2, 0, Pu, PuO and Pu02 as functions of temperature and of condensed phase composition. The calculated oxygen pressures increase rapidly as stoichiometry is approached. At least part of this increase is a consequence of the exclusion of Pu +... 

The temperature dependences of the total pressures In equilibrium with the condensed-phase composition PuOj gQ, PuOl.96> and P11O1.994 are compared in Figure 4. The differences shown In Figure 4 are due to the differences In oxygen pressures for the different compositions. 

During the course of exploratory experimentation involved in the preparation of 8-242pU203, some limited oxygen potential measurements over Pu02-X fluorite phase were made at 1750 and 2050 K. The transpiration method was used for this study because, for a given temperature, the composition of the condensed phase can be fixed by appropriate choice of oxygen potential (via H2/... 

One of the most Important thermophysical properties of reactor fuel In reactor safety analysis Is vapor pressure, for which data are needed for temperatures above 3000 K. We have recently completed an analysis of the vapor pressure and vapor composition In equilibrium with the hypostolchiometric uranium dioxide condensed phase (1 ), and we present here a similar analysis for the plutonium/oxygen (Pu/0) system. 

In this paper we describe (1) the gas-phase thermodynamic functions (2) the condensed-phase thermodynamic functions (3) the oxygen potential (and the phase boundaries that are consistent with It) and (4) the resulting vapor pressure and composition as functions of temperature and composition of the condensed phase. 

An alternative way to view the oxygen enrichment of the vapor relative to the condensed phase Is to calculate the oxygen-to-plutonium ratio of the gas, R(gas), with Eq. (2). The value of R(gas) exceeds that of the condensed phase with which It Is In equilibrium by a large amount. Like the U/0 system, this oxygen enrichment of the vapor relative to the condensed phase Is Increasing with temperature. One Implication of these results Is that the condensed-phase and vapor-phase compositions will depend upon the extent of vaporization of a sample with overall composition given by 0/Pu = 2 - x. 

The decrease of Si due to F-containing contaminants and the role of the oxygen plasma treatment can be explained by the principle of CAP. The key factor to explain the change of elementary composition at the interface is the plasma sensitivity of elements involved on the surface and in the plasma phase. The ablation of materials exposed to plasmas appears to follow the plasma sensitivity series of the elements involved, which is in the order of the electronegativity of the elements, i.e., elements with higher electronegativity in the condensed phase are more prone to ablate in plasma that contains elements with lower electronegativity [5]. 

Then, in the gaseous state, these small molecules react with oxygen, an exothermic step, producing carbon dioxide, water vapor, and other small molecules depending on the composition of the original polymer. Under fire conditions, part of the heat evolved is returned to the condensed phase polymer to continue the degrading process. 

Fire retardant additives may therefore act in various ways and in any one polymer/additive composition there may be more than one effect. Attention is limited here to effects (chemical or physical) on the polymer decomposition process and to examples of investigations in which the nature of the interaction as it affects the degradation mechanism of the polymer has been established. Some of the most detailed investigations have been made in the absence of oxygen this is appropriate, however, because it reflects the situation in the condensed phase from which the fuel is generated, since the oxygen is removed from the polymer surface by the burning fuel. 

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