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Barnes NR, Davis FJ, Mitchell GR. 1989. Molecular switching in liquid crystal elastomers. Mol Cryst Liq Cryst 168:13 25. Baughman RH. 1996. Conducting polymer arti cial muscles. Synth Met 78:339 353. Baughman RH, Cui C, Zakhidov AA, Iqbal Z, Barisci JN, Spinks GM, Wallace GG, Mazzoldi A, De Rossi D, Rinzler AG, Jaschinski O, Roth S, Kertesz M. 1999. Carbon nanotube actuators. Science 284:1340 1343. Bay L, West K, Sommer Larsen P, Skaarup S, Benslimane M. 2003. A conducting polymer arti cial muscle with 12% linear strain. Adv Mater 15:310 313. Beyer P, Zentel R. 2005. Photoswitchable smectic liquid crystalline elastomers. Macromol Rapid Commun 26:874 879. Brand HR, Finkelmann H. 1998. Physical properties of liquid crystalline elastomers. In: Handbook of liquid crystals. Demus D, Goodby J. Gray GW, Spiess HW, Vill V, editors. Weinheim: Wiley VCH. Brehmer M, Zentel R. 1994. Ferroelectric liquid crystalline elastomers. Macromol Chem Phys 195:1891 1904. Brodowsky HM, Boehnke UC, Kremer F, Gebhard E, Zentel R. 1999. Mechanical deformation behavior in highly anisotropic elastomers made from ferroelectric liquid crystalline polymers. Langmuir 15:274 278.

molecules to the electrode, their dissociation with simultaneous adsorption of atomic hydrogen on the electrode (reversed Tafel reaction (5.7.2)) and its subsequent oxidation. The shape of the polarization curve depends on which of these processes is slowest. The adsorption of hydrogen is affected by the adsorption of anions, occurring at positive potentials. The adsorbed anions, especially iodide, decrease both the adsorption energy and the maximal amount of hydrogen adsorbed. The effect of iodide is analogous to that of substances termed cathodic poisons, such as mercury ions, trivalent arsenic or cyanide ions. The retarding effect of adsorbed anions is especially apparent for the anodic ionization of hydrogen dissolved in solution at a platinum electrode. Figure 5.44 shows the voltammograms for this process at a rotating disk electrode. In the vicinity of the equilibrium potential, this process is controlled by convective diffusion (see Eqs 5.4.20 and 5.4.23); at slightly more positive potentials a limiting current appears that is then independent of the potential. At much more positive potentials, the surface process is retarded by the adsorption of sulphate anions and becomes the

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Broer DJ, Finkelmann H, Kondo K 1988 In situ photopolymerization of an oriented liquid crystalline acrylate Makromol Chem 189:185 194 Broer DJ, Boven J, Mol GN, Challa G 1989 In situ photopolymerization of oriented liquid crystalline acrylates Makromol Chem 190:2255 2268 Buguin A, Li MH, Silberzan P, Ladoux B, Keller P 2006 Micro actuators: when arti cial muscles made of nematic liquid crystal elastomers meet soft lithography J Am Chem Soc 128:1088 1089 Camacho Lopez M, Finkelmann H, Palffy Muhoray P, Shelley M 2004 Fast liquid crystal elastomer swims into the dark Nat Mater 3:307 310 Clarke SM, Hotta A, Tajbakhsh AR, Terentjev EM, 2001 Effect of cross linker geometry on equilibrium thermal and mechanical properties of nematic elastomers Phys Rev E 64:061702 Cotton JP, Hardouin F 1997 Chain conforation of liquid crystalline polymers studied by small angle neutron scattering Prog Polym Sci 22:795 828.

Fig. 5.44 The voltammogram of molecular hydrogen at a rotating bright platinum disk electrode in 0.5 M H2SO4, pHl = 105 Pa, 25 C. The rotation speed ^ ( s 1 ) is indicated at each curve. (According to E. A. Aykazyan and A. I. Fedorova)

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364 rate-controlling step in place of diffusion The higher the rotation rate of the electrode, the sooner the transition occurs between the transport-controlled process and the surface-controlled process The current increase at 16 V corresponds to platinum 'surface oxide' formation The electrocatalytic oxidation of lower aliphatic compounds such as alcohols, aldehydes, hydrocarbons and formic and oxalic acid at platinumgroup electrodes has a number of typical features The chemisorption process usually involves the dissociation of several hydrogen atoms from the original molecule and a so-far not completely identified intermediate (often termed 'reduced carbon dioxide' for the reactions of methanol, formaldehyde and formic acid) remains adsorbed on the electrode At electrode potentials higher than 035 V (versus a hydrogen electrode located in the same solution and saturated with hydrogen at standard pressure) all the hydrogen atoms formed during chemisorption are oxidized anodically.