Polymerization laser pulses

From this we can see that knowledge of k f and Rf in a conventional polymerization process readily yields a value of the ratio kp fkt. In order to obtain a value for kf wc require further information on kv. Analysis of / , data obtained under non-steady state conditions (when there is no continuous source of initiator radicals) yields the ratio kvlkx. Various non-stcady state methods have been developed including the rotating sector method, spatially intermittent polymerization and pulsed laser polymerization (PLP). The classical approach for deriving the individual values of kp and kt by combining values for kp kx. with kp/k, obtained in separate experiments can, however, be problematical because the values of kx are strongly dependent on the polymerization conditions (Section... 

It is noteworthy that nonlinearity of the absorption, required for 3D microfabrication can be provided via thermal mechanisms [53,54]. In the case of tightly focused laser pulses, linear absorption is most efficient at the focus, where local heating can create the conditions required for polymerization. Usually the absorption increases with temperature and thermal polymerization may become dominant at the focus. It is usually difficult to confirm the TPA mechanism from the direct transmission measurements due to the nar-... 

In addition to using imaging as a technique to obtain spatially and temporally patterned chemical data from a sample, one can also pattern chemical reactions in space and time using similar methods. Figure 2.18 demonstrates an example in which multiphoton scanning with ultrafast laser pulses was used to polymerize a photoresist resin with about 120 nm spatial resolution in three dimensions. 

The time to measure spectra of this quality under high-pressure conditions has been about I min. The absolute time scale of the experiment depends on the method of initiation. In thermally initiated (spontaneous) polymerizations reaction time can be several hours or even days. In contrast, in excimer laser-initiated free radical polymerizations application of a few laser pulses each of about 20 ns duration can induce changes between subsequent spectra as on this figure. 

A number of nonsteady polymerization rate techniques can be used to measure ftp [11]. The most widely used method involves pulsed-laser-induced polymerization in the low monomer conversion regime. Briefly, a mixture of monomer and photoinitiator (Section 6.5.3) is illuminated by short laser pulses of about 10 ns (10 sec) duration. The radicals that are created by this burst of ligh propagate for about 1 sec before a second laser pulse produces another crop of radicals. Many of the initially formed radicals will be terminated by the short, mobile radicals created in the second illumination. Analysis of the number molecular weight distribution of the polymer produced permits the estimation of ftp from the relation... 

The DR and AC intermediates of the photopolymerization reaction are stable only at low temperatures. At temperatures above about 100 K they react to form long macromolecules by subsequent addition of monomer molecules. The 10 K optical absorption spectra of Fig. 17 show the result of the thermal reaction as a function of the time at 100 K The initial spectrum showing only the dimer A absorption has been prepared at 10 K by only one UV-excimer laser pulse at 308 nm. Only pure thermal addition polymerization reactions are observed within the DR-series A, B, C,. .. No chain termination reactions are detectable in the optical spectra. The final product P is situated in the vicinity of the final polymer absorption. 

Figure 4. Examples of low-temperature limit of rate constant of solid-state chamical reactions obtained in different laboratories of the USSR, United States, Canada, and Japan (1) formaldehyde polymerization chain growth (USSR, 1973 [56]) (2) reduction of coordination Fe-CO bond in heme group of mioglobin broken by laser pulse (United States, 1975 [65]) (3) H-atom transfer between neighboring radical pairs in y-irradiated dimethylglyoxime crystal (Japan, 1977, [72], (4, 5) H-atom abstraction by methyl radicals from neighboring molecules of glassy methanol matrix (4) and ethanol matrix (5) (Canada, United States, 1977 [11, 78]) (6) H-atom transfer under sterically hampered isomerization of aryl radicals (United States, 1978 [73]) (7) C-C bond formation in cyclopentadienyl biradicals (United States, 1979 [111]) (8) chain hydrobromination of ethylene (USSR, 1978 [119]) (9) chain chlorination of ethylene (USSR, 1986 [122]) (10) organic radical chlorination by molecular chlorine (USSR, 1980 [124,125]) (11) photochemical transfer of H atoms in doped monocrystals of fluorene (B. Prass, Y. P. Colpa, and D. Stehlik, J. Chem. Phys., in press.).

Figure 3.91. Dependence of the crosslinked rod size of a TP polymerized acrylic acid ester on the laser pulse energy of a Ti sapphire femtosecond laser with a pulse width of 130 fs, a repetition rate of 5 kHz, and a wavelength of 800 nm that was obtained by doubling of 400 nm. (From Ref. [150] with permission of the American Institute of Physics.)...

Information about propagation and termination ( t) rate coefficients during a polymerization reaction are obtained from pulse sequence (PS)-PLP and single pulse (SP)-PLP experiments [21-23]. In the latter technique, monomer conversion is induced by a single excimer laser pulse typically of 20 ns width and is recorded by on-line vibrational spectroscopy with time resolution in the microsecond range. A typical monomer conversion versus time profile obtained for an ethene polymerization [24] at 190 °C, 2550 bar, and at 9.5 wt% polyethylene (from preceding polymerization) is shown in Figure 4.6-3. 

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