Polarity radiation-induced

The correct choice of solvents is essential to the success of radiation-induced graft copolymerization. Their influence on radiation grafting has been the subject of many studies. It has been established that solvents play an important role in grafting because of the significance of polymer swelling. The grafting patterns to PP are solvent-dependent, thus, it is essential to examine the role of solvents. It was found that grafting in the alcohol is better than when other polar solvents such as dimethyl-... 

This paper describes a method for improving hydrophilicity by using radiation-induced grafting of flexible polyurethane (polyether) foam with polar vinyl monomers. By this procedure, the normally hydrophobic material can be converted into a remarkably water-wettable sponge. 

The subject of 0(3) electrodynamics was initiated through the inference of the Bl]> field [11] from the inverse Faraday effect (IFF), which is the magnetization of matter using circularly polarized radiation [11-20]. The phenomenon of radiatively induced fermion resonance (RFR) was first inferred [15] as the resonance equivalent of the IFE. In this section, these two interrelated effects are reviewed and developed using 0(3) electrodynamics. The IFE has been observed several times empirically [15], and the term responsible for RFR was first observed empirically as a magnetization by van der Ziel et al. [37] as being proportional to the conjugate product x A multiplied by the Pauli matrix... 

The oscillating charge behaves like an antenna, and Equation (10) describes the field of such an antenna as long as r is large compared to the wavelength of the radiation that induces the oscillation. It should also be noted that the antenna to which Equation (10) applies is aligned vertically (z axis) and is therefore driven by vertically polarized radiation. 

This description of antennas may seem more appropriate to a discussion of radio or television waves. We must realize, however, that at the molecular level dipoles behave exactly like antennas. Since molecules are made up of charged parts, a dipole moment /x is induced by the electric field of the radiation in any material through which radiation passes. In this discussion, the dipole moment equals the product of the effective charge displaced by the field and its distance of separation from the opposite charge. In SI, pi has units C m. We consider isotropic materials characterized by a polarizability a. As the name implies, this property measures the ease with which charge separation —polarity —is induced in a molecule by an electric field. For isotropic substances, the dipole moment and the field are related by the expression... 

Optical response of a material is generally described in the approximation of electric-dipole interaction with the radiation ( 0. In this model, the oscillating electric field of radiation induces a polarization in the medium. When a material is subject to a strong optical pulse from a laser the electric field is intense and the... 

A polarization is induced in a material when subjected to laser radiation or dc electric fields. The following expression (1-3),... 

In non-polar liquids, then, the evidence seems conclusive that most of the electrons are recaptured by parent ions, at least in the absence of reactive scavengers, and that ionic processes therefore do not contribute significantly to the radiation-induced decomposition. However, in polar liquids where the electron could be solvated, the situation may be quite different. 

To reduce these effects, LDPE samples were cross-linked by e-beam irradiation and then subjected to the photosulfonation process. Compared to standard LDPE, crosslinked LDPE displayed a higher content of — SO3H groups and higher surface polarity after photosulfonation. This was evidenced both by zeta potential and contact angle measurements. It is thus demonstrated that sample pretreatment by crosslinking provides more stable surfaces which maintain their polar properties during water contact. This is explained by a lower amount of extractable components as a result of radiation-induced network formation. 

Cpl-induced asymmetric photochemistry is a way to conduct absolute asymmetric synthesis. The field is well developed. The method depends on the differential absorption of left and right circularly polarized radiation by the enantiomeric species of the reactants and thus on their g factor. The kinetic schemes are well developed, and for mechanistic questions as well as for the determination of molecular chiroptical constants cpl irradiation can be used with success. Unfortunately, the smallness of the enantiodifferentiating g factor prevents the method from being a match to the methods exploiting diastereomeric intermolecular interactions for thermal synthesis purposes. 

The extensive jt-delocalized system of metal-dithiolene complexes is also responsible for the nonlinear optical properties (NLO) which have been recently reviewed . The interaction of radiation with the matter induces an instantaneous displacement (polarization Pq = /X = aE, where a is the linear polarizability) of the electronic density away from the nucleus at small field (linear optics). At high fields (laser light) the polarizability of the molecule can be driven beyond the linear regime and a nonlinear polarization is induced (NLO) = aE + fiE" + y E + and for the bulk material... 

This result could explain differences in spectral data in the same systems obtained with low incidence angles (flat window) and high incidence angles (prismatic or spherical windows). The latter can furnish almost featureless spectra for solution species with s-polarized light (compare the curves in Fig. 12 at rf = 1 pm) and induce the wrong conclusion that no solution feature interferes in the spectra measured with p-polarized radiation [35-37]. On the contrary, the use of a flat window leads to comparable intensities for s- and p-polarized radiation spectra [27,38]. 

The origin of these effects lies in the polarization P induced in a molecule by a local electric field E (due to the electromagnetic radiation). P is expressed as a power series of the local field ... 

There seems little doubt that in radiation induced polymerizations the reactive entity is a free cation (vinyl ethers are not susceptible to free radical or anionic polymerization). The dielectric constant of bulk isobutyl vinyl ether is low (<4) and very little solvation of cations is likely. Under these circumstances, therefore, the charge density of the active centre is likely to be a maximum and hence, also, the bimolecular rate coefficient for reaction with monomer. These data can, therefore, be regarded as a measure of the reactivity of a non-solvated or naked free ion and bear out the high reactivity predicted some years ago [110, 111]. The experimental results from initiation by stable carbonium ion salts are approximately one order of magnitude lower than those from 7-ray studies, but nevertheless still represent extremely high reactivity. In the latter work the dielectric constant of the solvent is much higher (CHjClj, e 10, 0°C) and considerable solvation of the active centre must be anticipated. As a result the charge density of the free cation will be reduced, and hence the lower value of fep represents the reactivity of a solvated free ion rather than a naked one. Confirmation of the apparent free ion nature of these polymerizations is afforded by the data on the ion pair dissociation constant,, of the salts used for initiation, and, more importantly, the invariance, within experimental error, of ftp with the counter-ion used (SbCl or BF4). Overall effects of solvent polarity will be considered shortly in more detail. 

A major difference between the two methods of initiation is that the solvent in y-ray studies is almost inevitably the monomer itself, and these generally have lower dielectric constants than the chlorocarbon solvents most often used in the chemically initiated systems. As a result, it is not possible to compare the values of kp +) obtained from each technique without accounting for this difference in solvation. Classically, propagation involves charge dispersion in forming the transition-state complex and hence a reduction in the polarity of the system. Thus media of lower solvation power should favourably influence the process. (See reference 114 for more detailed discussion.) Experimentally the values of kp(+) from radiation-induced polymerizations are consistently higher than those obtained using stable salts as initiators, and this simplistic picture therefore seems to be confirmed. Dunn has recently carried out a detailed compilation of the available data on / p(+) and readers will find this an excellent distillation of the current position. 

Because circular dichroism is a difference in absorption for left and right circularly polarized light, its theoretical description includes subtraction of the transition probabilities induced by left and right circularly polarized radiation. The interaction Hamiltonian that determines transition probability includes electric, , and magnetic, B, fields of electromagnetic circularly polarized radiation, and the electric, /i, and magnetic, m, dipole moments of the molecule. 

Fig. 1. Detector elements and readout circuitry, (a) Hypothetical implementation of the full-array microscope architecture (b) THz radiation induced electron polarization and the scheme of communication for future integration of the arrays (c) RF measurement of the polarization of the trapped electron in the detection cell.

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