Scission rate diffusion

Overall, therefore, the available literature supports the generally held view that the durability of UF-bonded wood products is governed by the susceptibility of cured UF resin bonds to scission by both hydrolysis and swell/shrink stresses. Note, moreover, that in either case, the most likely product of scission will ultimately be formaldehyde and further that mechanical stress enhances the rates of many chemical reactions (37). In fact, simplistic calculations based on formaldehyde liberated from bond ruptures at least indicate the possibility that formaldehyde from swell/shrink stress rupture could contribute significantly to total emission. Assume, for example, that board failure occurs due to rupture of one chemical bond type which liberates one molecule of formaldehyde and consider two cases (a) a conservative one in which only 5 percent of those bonds rupture in 50 years, i.e., probable board durability greater that 50 years, and (b) a much less conservative case in which 30 percent of those bonds rupture in 20 years, i.e., probably failure in 20 years or less. Case (a) leads to a first order scission rate constant of 3.3 x 10 s and a hypothetical board emission rate (see Appendix 3a) that is below the maximum liberation rate permitted by the German E-1 standard (7). However, Case (b) leads to a first order scission rate constant of 5.7 x 10 s and a hypothetical board emission rate above that allowed by the HUD standard (8). (FormaIdehyde-wood interactions and diffusion effects would... 

Diffusion processes are ignored in the model presented in this chapter which could be important. For example, if diffusion of the calcium and phosphate ions in the polymer phase is slow comparing with the polymer scission rate, then the model would over-predict the effect of the TCP phase and hence under-predict the degradation rate. On the other hand, if the short chains can diffuse out of the device quickly such as in a very thin sample, then the TCP phase will be less useful and the model will over-predict the degradation rate of the polymer. It is possible to build these diffusion processes into the model to analyse aU the different possible scenarios. 

Scission rate of long chains affected by short chain diffusion... 

For semi-crystalline polymers, the governing equation for chain scission rate and short chain diffusion are... 

EB irradiation of polymeric materials leads to superior properties than the 7-ray-induced modification due to the latter having lower achievable dose rate than the former. Because of the lower dose rate, oxygen has an opportunity to diffuse into the polymer and react with the free radicals generated thus causing the greater amount of chain scissions. EB radiation is so rapid that there is insufficient time for any significant amount of oxygen to diffuse into the polymer. Stabilizers (antirads) reduce the dose-rate effect [74]. Their effectiveness depends on the abUity to survive irradiation and then to act as an antioxidant in the absence of radiation. 

Alkoxy (R0 ) radicals react at near diffusion controlled rates with trialkyl phosphites to give phosphoranyl radicals [ROP(OR )3] that typically undergo very fast -scission to generate alkyl radicals (R ) and phosphates [OP(OR )3]. In a mechanistic study, trimethyl phosphite, P(OMe)3, has been used as an efficient and selective trap in oxiranylcarbinyl radical systems formed from haloepoxides under thermal AIBN/n-Bu3SnH conditions at about 80 °C (Scheme 27) [64]. The formation of alkenes resulting from the capture of allyloxy radicals by P(OMe)3 fulfils a prior prediction that, under conditions close to kinetic control, products of C-0 cleavage (path a. Scheme 27), not just those of C-C cleavage (path b. Scheme 27) may result. 

The second phase of polymer degradation is characterized by a decrease in the rate of chain scission (Fig. 19) and the onset of weight loss. Weight loss has been attributed to (1) the increased probability that chain scission of a low molecular weight polymer will produce a fragment small enough to diffuse out of the polymer bulk and (2) the breakup of the polymer mass to produce smaller particles with an increased probability of phagocytosis. The decrease in the rate of chain scission, as well as the increased brittleness of the polymer, is the result of an increase in the crystallinity of PCL,... 

Much research into radiation effects on polymers is done with samples sealed under vacuum. However, polymer materials may, in practical applications, be subjected to irradiation in air. The effect of irradiation is usually substantially different in air, with increased scission at the expense of crosslinking, and the formation of peroxides and other oxygen-containing structures. Diffusion rates control the access of oxygen to radicals produced by the radiation, and at high dose rates, as in electron beams, and with thick samples, the behaviour may be similar to irradiation in vacuum. Surface changes may be quite different from bulk due to the relative availability of oxygen. 

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