Irradiation effects precipitation

Nguyen and Kausch [1984] found that the presence of phenyl groups in poly(styrene-co-acrylo-nitrile), SAN, protects PMMA in the blend, during radiolysis (Table 11.9). SAN and PMMA were dissolved in dimethyl formamide, 50- J,m-thick films were cast, and then dried under vacuum. Transparent bar specimens were compression-molded from the film. Mixing the polymers by co-precipitation from methanol resulted in opaque samples. Gamma irradiations were done in evacuated and sealed glass tubes, at a dose rate of 3 kGy/h. Comparison of freshly irradiated samples with irradiated and annealed ones showed the absence of any post-irradiation effects. 

Irradiation effects and microstructural changes in Generation IV reactor materials have been discussed in this chapter. The role of irradiation-induced point, hne, and volume defects in performance of steels has been discussed and radiation-induced segregation and precipitation mechanisms have been dehneated. New characterization techniques recently deployed in the nuclear materials field have been introduced and advantages and limitations of each technique have been provided. 

The auto-acceleration observed under such conditions is reduced ( = 1.15) and could partially result from non-steady-conditions but also from a "matrix effect" operating on the surface of unswollen polymer particles. It should be noted in this respect that the post-polymerization which is induced by the growing chains occluded in the precipitated polymer exhibits an initial rate very much lower than the rate observed during irradiation (Curve 1 in Figure 91 which suggests that the contribution of the growth of occluded chains to the over-all rate is small. 

DASPE-TFPB), respectively. The obtained solid precipitates were brightly emissive whereas that of the native DASPE-I were almost nonemissive (Fig. 7a the photo is taken under normal illumination and UV-light irradiation). This indicates that, in the solid of the ion-pair species between DASPE+ and TPB (or TFPB ), concentration quenching is effectively suppressed, and more importantly, these ion-pair complexes can generate fluorescent... 

Miodownik et al. 1979, Watkin 1979). Irradiation can cause void-swelling, suppression of a formation in stainless steels and non-equilibrium precipitation of silicides. These phenomena are complex and occur by a combination of thermodynamic and kinetic effects. However, it was shown by Miodownik et al. (1979) that a thermodynamic analysis could be used to good effect to rationalise the effect of radiation on silicide formation. Although the work was done for a simple alloy system, it demonstrates how thermodynamics can be used in unusual cirounstances. 

The uranium and thorium ore concentrates received by fuel fabrication plants still contain a variety of impurities, some of which may be quite effective neutron absorbers. Such impurities must be almost completely removed if they are not seriously to impair reactor performance. The thermal neutron capture cross sections of the more important contaminants, along with some typical maximum concentrations acceptable for fuel fabrication, are given in Table 9. The removal of these unwanted elements may be effected either by precipitation and fractional crystallization methods, or by solvent extraction. The former methods have been historically important but have now been superseded by solvent extraction with TBP. The thorium or uranium salts so produced are then of sufficient purity to be accepted for fuel preparation or uranium enrichment. Solvent extraction by TBP also forms the basis of the Purex process for separating uranium and plutonium, and the Thorex process for separating uranium and thorium, in irradiated fuels. These processes and the principles of solvent extraction are described in more detail in Section 65.2.4, but the chemistry of U022+ and Th4+ extraction by TBP is considered here. 

A mixture of 3-chloroaniline le (2.10 mL, 20.0 mmol) and diethyl phenylmalo-nate 2e (8.62 mL, 40.0 mmol) is stirred and irradiated in a microwave oven (type Milestone Ethos 900) for 15 min at 500 W power under a gentle stream of nitrogen (in order to effectively remove the formed ethanol during the reaction). The mixture is allowed to attain room temperature and diluted with diethyl ether. The precipitate is collected by filtration and washed with diethyl ether to furnish pure 7-chloro-4-hydroxy-3-plienylquiiiolin-2(l//)-one 3e (4.36 g, 81%) as white crystals. 

Although the process proved satisfactory from the chemical standpoint, practical problems emerged in that the hydraulic operation of the mixer-settler batteries was extremely poor. In effect, as soon as the aqueous solutions from the dissolution of irradiated targets were placed in contact with the organic extraction phases, a stable emulsion was formed, produced by the appearance of extensive precipitates at the aqueous solution/organic solution interface. As no chemical remedy was found to solve this problem, we attempted to adapt this type of process to extraction chromatographic techniques. 

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