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whre d = q p is the thickness of the liquid junction. Although the Henderson formula depends on a number of simplifications and also employs ion concentrations rather than activities, it can nonetheless be used for estimation of the liquid junction potential up to moderate electrolyte concentrations, apparently as a result of compensation of errors. If there is only a single uni-univalent electrolyte with a common anion or cation on both sides of the liquid junction and the concentration of both electrolytes is the same, e.g.

Parallel grating (b)

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solution 1 solution 2 then Eq. (2.5.34) is reduced to the form (Lewis-Sargent equation)

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Figure 11.7. Schematic illustration of (a) the anisotropic morphology of stretched SBS and (b) the periodic presence of disordered cis-azobenzene and oriented trans-azobenzene in irradiated and nonirradiated fringes, respectively, for both perpendicular and parallel gratings recorded on azo-SCLCP-grafted SBS. Source: Bai and Zhao, 2002. Reprinted with permission.

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the SBS as a background, the probe light sees different refractive indices, n|| and n>, with its polarization parallel or perpendicular to the strain, respectively As for the azobenzene polymer, in both parallel and perpendicular gratings, irradiated areas mainly contain disordered cis-azobenzene and nonirradiated areas contain oriented trans-azobenzene If the SBS background undergoes no changes initiated by photoisomerization of azobenzene in irradiated areas, the difference in refractive index between irradiated and nonirradiated fringes should mainly arise from differences between disordered cis-azobenzene and oriented trans-azobenzene However, the diffraction ef ciency should also be polarization-dependent When the probe light is polarized with its electric vector parallel to the strain, light sees the extraordinary refractive index of trans-azobenzene, ntrans, in nonirradiated areas and e the average refractive index of cis-azobenzene, ncis, in irradiated areas.

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where the symbols 1 and 2 designate the electrolytes in solutions 1 and 2 and the A's are the molar conductivities at the given electrolyte concentrations. The minus sign holds when the electrolytes have a common anion and the plus sign holds for a common cation. The Henderson equation for a constantly varying electrolyte mixture approximately approaches conditions for a liquid junction with free diffusion (see Fig. 2.13). The general Planck's solution of the liquid-junction potential is based on the assumption that the fluxes of ions in the liquid junction are in a steady state. As the mathematical treatment is rather space-consuming the reader is recommended to inspect a more recent treatment of this by W. E. Morf

In contrast, if the polarization of light is perpendicular to the strain, light senses the ordinary trans refractive index of trans-azobenzene, no , in nonirradiated areas and, still, ncis in irradiated areas In the latter case, the diffraction ef ciency is smaller because the trans difference between no and ncis is smaller than the difference between ntrans and ncis e As is shown later, this feature indeed was observed The tunable feature of such an elastic grating is shown by the polarizing optical micrographs (POMs) in Fig 118 On a lm stretched to 300% extension (thickness B10 mm under strain), two gratings with 10-mm fringe spacing were recorded parallel and perpendicular, respectively, to the SD using a photomask (360-nm UV irradiation of intensity B2 mW/cm2, 10-min exposure) (Fig 118a) The irradiated areas, including an uncovered region between the two photomasks, appear dark.

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Fig. 2.13 Examples of liquid junctions: (A) liquid junction with 'free' diffusion is formed in a three-way cock which connects the solution under investigation with the salt bridge solution; (B) liquid junction with restrained diffusion is formed in a ceramic plug which connects the salt bridge with the investigated solution

The stretched lm was then allowed to retract to its half-length (Fig 118b); the fringe spacing of the perpendicular grating decreases, while it increases for the parallel one Gratings can be inscribed at any alignment with respect to SD, which result in different changes in fringe spacing upon elastic extension and retraction of the lm Using the grating with fringes perpendicular (grating vector parallel) to SD, the rst-order diffraction of light was measured as a function of draw ratio de ned as the lm length after stretching over that before stretching Figure 119 shows the measured diffraction angle, Y, as well as the fringe spacing, L, calculated according to L = l/(2 sin Y), l being the wavelength of the used probe light (an He Ne laser operating at 633 nm).

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