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These equations are general and apply equally for multifunctional reactions such as that of A B. Af with Bf or that of Af with A and B Depending on which of these reactant combinations is involved, the value of a will be appropriately determined by the parameters r, f , p, and r. For convenience the size distributions in the reaction of equivalent amounts of trifunctional reactants alone, that is, where a p, will be considered. A comparison of Eqs. 2-89 and 2-166 shows that the weight distribution of branched polymers is broader than that of linear polymers at equivalent extents of reaction. Furthermore, the distribution for the branched polymers becomes increasingly broader as the functionality of the multifunctional reactant increases. The distributions also broaden with increasing values of a. This is seen in Fig. 2-17, which shows the weight fraction of x-mers as a function of a for the polymerization involving only trifunctional reactants.



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Fig. 2-17 Molecular weight distribution as a function of the extent of reaction for the polymerization of trifunctional reactants where a p. After Flory [1946] (by permission of American Chemical Society, Washington, DC).





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R Senitzky Semiclassical method and zero-point oscillations Physical Review Letters, 20(19):1062-1065, May 6,1968 557 I R Senitzky Radiation-reaction and vacuum-field effects in Heisenbergpicture quantum electrodynamics Physical Review Letters, 31(15):955-958, October 8,1973 558 J H Shapiro, H P Yuen, and J A Machado Mata Optical communication with two-photon coherent states: II Photoemissive detection and structured receiver performance IEEE Transactions on Information Theory, IT-2S(2):179-192, March 1978 559 B W Shol'e and P L Knight TbeJaynes-Cummingsmodel JournalofModern Optics, 4O(7):1195-1238,July 1993 560 A E Siegman Lasers University Science Books, Mill Valley, CA, 1986 561 A E Siegman Excess spontaneous emission in non-Hermitian optical systems: I Laser amplifiers Physical Review A, 39(3): 1253-1263, February 1, 1989 562 A E Siegman Excess spontaneous emission in non-Hermitian optical systems: II Laser oscillators Physical Review A, 39(3):1264-1268, February 1, 1989 563 A E Siegman Laser beams and resonators: The 1960s.

Fig. 2-18 Weight fractions of various nite species and of gel in a trifunctional polymerization where a p. After Flory [1946] (by permission of American Chemical Society, Washington, DC).

IEEE Journal of Special Topics in Quantum Electronics, 6(6): 1380-1388, November-December 2000 Online on Siegman's home page: http://www-eestanfordedwsiegman..

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Figure 2-18 shows a plot of the weight fraction of different x-mers versus a or p for the trifunctional polymerization The weight fraction wgel of the gel or 1-mer is also plotted A comparison of Figs 2-17 and 2-18 with Fig 2-9 for linear polymerization shows that the weight fraction of monomer is always greater than that of any one of the other species (up to the point where the curves for w1 and wgel intersect) As the reaction proceeds, larger species are built up at the expense of the smaller ones, and a maximum is reached at a value of p less than 1 The maximum shifts to higher values of p for the larger species The dis2 tribution broadens and reaches maximum heterogeneity at the gel point a 1 , where the 2 fraction of species that are highly branched is still small.

564. L. Silberstein. Elektromagnetische Grundgleichungen in bivectorieller Behandlung. Annalen der Physik, 22:579.1907. 565. L. Silberstein. Nachtrag zur Abhandlung fiber "Elektromagnetische Grundgleichungen in bivectorieller Behandlung". Annalen der Physik, 24:783, 1907. 566. L. Silberstein. Quaternionic form of relativity. Philosophical Magazine, 23(137): 790-809, May 1912. Online at http://home.pipeline.comFhbakerllquaternionl. 567. C. C. Silva and R. de Andrade Martins. Polar and axial vectors versus quaternions. American Journal of Physics, 70(9):958-963, September 2002. 568. J. E. Sipe. Photon wave functions. September 1995.

The in nite network polymer is rst formed at the gel point, and its weight fraction rapidly increases The species in the sol (consisting of all species other than gel) decrease in average size because the larger, branched species are preferentially tied into the gel Past the point of intersection for the w1 and wgel curves gel is the most abundant species on a weight basis The broadening of the distribution with increasing a can also be noted by the X w =X n value Equations 2-167 and 2-169 show that the difference between the number- and weight-average degrees of polymerization increases very rapidly with increasing extent of reaction At the gel point the breadth of the distribution X w =X n is enormous, since X w is in nite, while X n has a nite value of 4 (Fig 2-19).

Physical Review A, 52(3):1875-1883,

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