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is assigned a zero value by convention (as mentioned above, this value is assigned to a point infinitely far away from all the conductors), then we can say that potentials or, and ip are measurable just as if they were absolute values. However, both the inner potential and the Galvani potential difference cannot be measured in the sense of 'absolute' values using purely thermodynamic procedures. As a function of the surface potential %, the electron work function for a given material depends on the state of the surface of that material (adsorption, the presence of surface compounds, etc.). For crystalline substances (see Table 3.1), various crystal faces have various electron work function values, which can be measured for single crystals. For poly crystalline substances, the final value of the electron work function depends on the contribution of the individual crystal faces to the entire area of the phase and the corresponding electron work functions; the final value of the work function, however, is strongly dependent on the experimental method used for the measurement. The electron work function is very important for the physics of the solid phase and for its application to electronics. In electrochemistry, it is especially important for electrode processes involving adsorption of some of the species participating in the electrode reaction. If two different, electrically uncharged phases are brought into contact, then the electrochemical potentials of their electrons become equal (i.e.
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Scheme 12.8 Preparation of azo BCs by using living cationic polymerization and free-radical polymerization techniques. Source: Reproduced from Serhatli and Serhatli, 1998.
13
vacuum free surface phase a phase (5
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the immiscibility between the azo blocks and non-azo blocks. As shown in Fig. 12.2, all the processes in the microphase separation at different temperatures might be in uenced by the azo photoisomerization, andthe microphase-separated nanostructures in azo BC lms could have effect on the photochemical behavior of azo blocks and vice versa (Cui et al., 2003). The photochemical control and supramolecular self-assembly make the azo BCs in solid state superior to that of azo homopolymers or azo random copolymers. On the one hand, the azo BCs inherit most of the excellent properties of azo homopolymers (Ichimura, 2000), such as trans cis photoisomerization, photoselective alignment with azo transition moments almost perpendicular to the polarization direction of the actinic light, and photochemical phase transition, since the trans-azo can be a mesogen because its molecular shape is rodlike, whereas the cis-azo never shows any LC phase because of its bent shape. All the illustrations of the photosensitive performances are shown in Fig. 12.3 (Yu et al., 2005a).
Fig. 3.5 The significance of the contact potential (Volta potential difference) A V between two metals in contact. (According to S. Trasatti and R. Parsons)
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their Fermi levels are brought to the same level see Fig. 3.2). An electrical double layer is formed on the contact surface and the outer potentials of the free surfaces of both phases attain different values; i.e. a Volta potential difference (contact potential) is formed between them see Fig. 3.5. Measurement yields both the differences between the outer potentials and the work functions (real potentials). If two phases oc an / with a common species (index i) come into contact, at equilibrium &(<*) = /*, (/}), that is (Xi{a) ai(P) = ZiFApij). These quantities are mostly measured using the vibrating condenser, thermoionic, calorimetric, and photoelectric methods. The principle of the vibrating condenser method, originally proposed by Thomson, is depicted in Fig. 3.6. Space A between the metal phases a, a'
Supramolecular self-assembly in azo BC films Azo BC in isotropic melt Order disorder transition Microphase separation Temperature T > TLC Rubbery or LC T > Tg Vis, trans Glassy, crystal, or LC Glassy or LC UV Rubbery or LC T > Tg T > Tm
Fig. 3.6 Thomson's vibrating condenser method. A, space filled with an inert gas at low pressure; P, potentiometer; G, null instrument
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Figure 12.2. Microphase separation and azo photoisomerization in bulk lms of well-de ned azo BCs. TLC is LC isotropic phase transition temperature.
156 and / is filled with an inert gas at very low pressure. Phases a and / are in contact. Phases a and oc' are chemically identical. As they are surrounded by the same medium, x(a) = X(a') an< ^ b th the chemical potentials and the electron work functions are identical for both these phases, that is jUe(ar) = jUe(ar'); ac(a) = ae(a'). The outer potentials of phases a' and (3 are different, reflected in the fact that current flows through galvanometer G on a change in the distance between oc' and /3 or on ionization of atoms of the gas (e.g. by irradiation with a radioactive substance) in space A. This current can be compensated by the voltage U derived from potentiometer P, for which U = 4>(a) - 0("') = -F-\jie(*) fie(a')) (3.1.30)
Figure 12.3. Properties of azo BCs inherited from azo homopolymers. A is the absorption of azo chromophores, y represents the angle between the polarization direction of the linearly polarized light and the transition moment of an azo moiety.
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