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nonuniform This problem is more severe for reactions carried out at high values of [A] and a because the variation of Rp with D is greater for larger values of [A] and a [Lee et al, 2001] Uniformity of polymerization is increased by using lower concentrations of photoinitiators with lower a values However, there is a tradeoff between polymerization rate and uniformity of reaction The nonuniformity of polymerization with depth of penetration is less for photobleaching photoinitiators compared to photoinitiators that are regenerated Photobleaching allows photon penetration deeper into the reaction system The nonuniformity of polymerization with depth of penetration is also minimized (but not completely overcome) by using a mixture of two photoinitiators (or one photoinitiator) with absorption bands at two different wavelength, one of which absorbs strongly (large a) and the other weakly (small a).



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To see the patterns that develop in our one-dimensional string resonator, we will simply remove the driving force and assume that we have somehow set the string in oscillation so that it oscillates as a perfect sine at a point x = Xo: for example,.

Click in the cell where you want to insert a sum total. Click the Formulas tab on the Ribbon. Click the AutoSum button.





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The strong absorption band gives a high intensity at the surface of the reaction system, but the intensity rapidly decreases with penetration The intensity of the weak absorption band is less effected by penetration and provides a more uniform intensity as a function of penetration Dual photothermal initiation systems are also used The speci c photoinitiator initiates rapidly enough to generate suf cient heat to drive a thermal polymerization within the depth of the reaction system Performing photopolymerizations in air, which would simplify commercial practice, has a major complication due to two effects of oxygen Oxygen acts as quencher of photoexcited states of molecules and also inhibits polymerization by its reaction with radicals (Sec 3-7b) This problem can be avoided by performing the photopolymerization under an inert atmosphere (nitrogen, argon).

y(xo, t)

Using a protective coating of a paraf n oil or some other compound has also been reported [Padon and Scranton, 2000] These methods are usually avoided because of cost and other practical considerations The use of an appropriate two-wavelength photoinitiator system overcomes the oxygen problem by having a higher intensity energy absorption in the surface layer 3-4d Initiation by Ionizing Radiation.

(2.84)

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Radioactive sources and particle accelerators are used to initiate polymerizations. Electrons, neutrons, and a-particles (He2 ) are particulate radiations, while gamma and X rays are electromagnetic radiations. The interactions of these radiations with matter are complex [Chapiro, 1962; Wilson, 1974]. The chemical effects of the different types of radiation are qualitatively the same, although there are quantitative differences. Molecular excitation may occur with the subsequent formation of radicals in the same manner as in photolysis, but ionization of a compound C by ejection of an electron is more probable because of the higher

As there is no driving force, the displacement satisfies (2.74). Then the general solution24 must be of the form

3-57

y(x, t)

energies of these radiations compared to visible or ultraviolet light energy. (Ionizing radiations have particle or photon energies in the range 10 keV 100 meV (1 16,000 fJ) compared to 1 6 eV for visible ultraviolet photons.) For this reason such radiations are termed ionizing radiations. The cation formed in Eq. 3-67 is a radical cation C formed by loss of a p-electron and has both radical and positive centers (Sec. 5-2a-6). The radical cation can propagate at the radical and/or cationic centers depending on reaction conditions. The radical cation can also dissociate to form separate radical and cationic species:

~]).

3-58

(2.85)

The initially ejected electron may be attracted to the cation B with the formation of another radical:

AutoSum generates a formula to total the adjacent cells. or click Enter ( ).

3-59

22The previous solution can be recovered by taking the limit L ..... 00 and then f ..... 0 (Problem 2.8). 23In fact, this standing wave can be written as the sum of two traveling waves: one that travels to the right and another that travels to the left. 24The solution obtained by imposing only the boundary conditions y( -L/2, t) = y(L/2, t) = O.

Radicals may also be produced by a sequence of reactions initiated by the capture of an ejected electron by C

FIAT LUX!

3-60 3-61 3-62

At x = Xo (2.85) must coincide with (2.84):

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aspose convert pdf to word c#

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