Polysaccharide Film Technologies: Interfacial Order and Chain Thermodynamic Rigidity

Grishchenko, A. E.

doi:10.1080/02648725.1999.10647983

Cited by 10 publications

(10 citation statements)

References 21 publications

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“…However, as is seen from Figure 4, the best fit to the experimental data 23,24 is reached with the function S 0 (A) calculated according to eq 5 at the same value of the interchain interaction parameter, b = 1.75 for different polysaccharide structures and b = 1.1 for phenyl-containing sulfonated polymers. [35][36][37] Thus, on the one hand, different chemical microstructure and orientations of monomers (Figure 1) lead to the formation of chains with substantially different equilibrium characteristics.…”

Section: Statistical Properties Of Infinitely Extended Systemsmentioning

confidence: 84%

“…In the theory of the tilted polarized-beam technique based on birefringence measurement, [20][21][22][23][24][25] defined by the relationship…”

Section: Appendix C: Measurements Of Spontaneous Surface Birefringencementioning

confidence: 99%

“…where N A is Avogadro's number, n is the refractive index of the polymer, λ is the wavelength of incident light, (a ) a ^) is the difference of the principal components of optical polarizability of the monomer unit, M 0 is its molecular mass, F is the density of the polymer, H is the film thickness, and H 0 is the total effective thickness of optically anisotropic film surface layers characterizing the distance from the film surface at which the orientational order parameter decreases by a factor of e relative to S 0 (table 2, column 4). 22,23 The measurements of spontaneous birefringence by means of the tilted incidence polarized-beam technique 20,22 showed that the surface birefringence B for polysaccharides first linearly increases with an increase in the film thickness H and then tends to the limiting value B 0 (Figure 6). Therefore, in accordance with eq C1, the experimental plots B(H ) in refs 22-24 were extrapolated by the relation…”

Section: Appendix C: Measurements Of Spontaneous Surface Birefringencementioning

confidence: 99%

“…[20][21][22][23][24][25] In general, when the range of angle γ n is 125.3°> γ n > 54.7°the chains are oriented predominantly in the plane of film surface; when 54.7°> γ n > -54.7°, the chains are largely arranged normally to the surface. 23 It is necessary to mention that the orientational order parameter P 0 determines dielectric properties of chains with oriented dipole moments directed along the chain segments in polar polymer systems, whereas the relaxation of quadrupole orientational order parameter S 0 determines the luminescence depolarization for a chain containing a marker with an oscillator directed along the axis of the chain segment. This parameter may be also related to nuclear magnetic relaxation or measurement of spontaneous birefringence.…”

Section: Introductionmentioning

confidence: 99%

“…Parameter P 0 = S 0 = 0 in the isotropic state with random orientation of chain segments and P 0 → 1 and S 0 → 1 in strongly axially ordered systems, for example, in ferroelectric and nematic phases accordingly. In polymer films when S 0 = −0.5, the perfect planar-chain ordered system is observed. − In general, when the range of angle γ n is 125.3° > γ n > 54.7° the chains are oriented predominantly in the plane of film surface; when 54.7° > γ n > −54.7°, the chains are largely arranged normally to the surface . It is necessary to mention that the orientational order parameter P 0 determines dielectric properties of chains with oriented dipole moments directed along the chain segments in polar polymer systems, whereas the relaxation of quadrupole orientational order parameter S 0 determines the luminescence depolarization for a chain containing a marker with an oscillator directed along the axis of the chain segment.…”

Section: Introductionmentioning

confidence: 99%

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Orientational Order in Nanolayers of Cast Polymer Films

Maksimov

Kusheva

2009

Langmuir

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The spontaneous ordering of fragments of chain molecules near the surface in polymer films is described in terms of the multichain model, which allows for local intra- and interchain segment orientational interactions, as well as for transversal fluctuation of their orientation as an approximation of strong planar orientation order in the layers. Chain packing in the plane-ordered state is impossible unless the interchain interaction parameter has a critical value. This value decreases with chain bending rigidity. The calculated dependences of the limiting values of the quadrupole orientation order parameter on the length of the Kuhn statistical segment describe reasonably well the experimental data obtained in a study of polymer homologue polysaccharides and sulfonated phenyl-containing polymers. The monolayer thickness in films of some polysaccharides and sulfonated phenyl-containing polymers has been calculated from the fit of the theoretical to the experimental data of the surface birefringence on the number of nanolayers.

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Section: Statistical Properties Of Infinitely Extended Systemsmentioning

confidence: 84%

“…In the theory of the tilted polarized-beam technique based on birefringence measurement, [20][21][22][23][24][25] defined by the relationship…”

Section: Appendix C: Measurements Of Spontaneous Surface Birefringencementioning

confidence: 99%