¹
a) B. Wessling, DE 34 22 316 and corresponding international patents (Zipperling Kessler & Co.)
b) B. Wessling, Ad. Mater. 5 (4), 300 - 305 (1993)

² the first reports of "soluble" and "moldable" conductive polymers were published by

R. L. Elsenbaumer, K. Jen, R. Obodi, Polym. Master. Sci. Eng. 53, 79 (1985)

R. L. Elsenbaumer, K. Jen, R. Obodi, Synthetic Metals 15, 169 (1986)

³L. Shacklette, C. Han, "Solubility and dispersion characteristics of Polyaniline", Mat. Res. Soc: Symp. Proc. 328, 157 - 166 (1994), a paper in which the authors tried to determine the solubility parameter of polyaniline, emeraldine base and salt (EB, ES)

⁴for entering this field of science, many textbooks are available, like

a) S. Ross, I. Morrison: "Colloidal Systems and Interfaces", J.- Wiley 1988

b) D. Everett "Basic Principles of Colloid Science", Royal Society of Chemistry, 1988

from which I took some ideas for this paragraph

⁵for a deeper discussion, cf. any good textbook about macromolecular science

⁶ quantitative figures are generally rare in the field of solution or dispersion properties, and - if available - differing; as it is not the goal to calculate precisely but to support qualitative arguments by appropriate data; they are taken as average numbers from tables being found in

- R. Weast, M. Astle (eds.) Handbook of Chemistry and Physics, 62nd edition, CRC press 1981

- A. Barton, Handbook of Solubility Parameters and other Cohesion Parameters, CRC Press1985

- J. Brandrup, E. Immergut (eds.), Polymer Handbook 2nd edition, J. Wiley 1975

⁷R. Pelster, G. Nimtz, B. Wessling, Phys. Rev. B 49, 12718 - 12 723

⁸G. Nimtz, P. Marquardt, H. Gleiter, J. Cryst. Growth, 86, 66 (1988)

P. Marqurdt, G. Nimtz, Phys. Rev. B, 40, 7996 (1989)

⁹Hollemann, Wiberg "Anorganische Chemie", W. de Gruyter, 1971

¹⁰Cotton, Wilkinson, "Anorganische Chemie", Verlag Chemie 1970

¹¹this value was estimated by using the Born-Haber cycle for HCl (gas) using known values.

¹²Y. Fu, R. Elsenbaumer, Chemistry of Materials (Am. Chem. Soc.) 6 (5), 671 (1994)

¹³B. Wessling, Synthetic Metals 45, 119 - 145 (1991)

¹⁴B. Wessling, Z. Phys. Chem. 191, 119 - 135 (1995)

¹⁵see [6], ref. c) Handbook of Chemistry and Physics

¹⁶E. Bosch, Z. Phys. 137, 89 - 103 (1954)

¹⁷B. Wessling, Polym. Sci. Engin. 31 (16), 1200 - 1206 (1991) and also cf. [2]; for a broader discussion of dissipative structures in such systems, cf. B. Wessling, in: S. Nalwa (ed.) Handbook of Organic Conductive Molecules and Polymers, Vol III, J. Wiley (in press)

¹⁸B, Wessling, Synthetic Met. 41-43, 907 - 910 (1991)

¹⁹and analogous for PAni with other counter-ions than HCl, provided that the monomer/counterion relation is 0.5, so that no shell of detergent-like counterions forms, as is the case with DBSA, CSA and others.

²⁰In the meantime we have succeeded in preparing several different types of stable water dispersions of polyaniline, but only by using a non-conventional approach; cf. data sheet Ormecon Chemie

²¹P. Kinlen, ICSM 1996 Snowbird/USA, Synthetic Met., in press

²²XICP-OS01, Experimental Product Data Sheet, Monsanto, 1996

²³"Neste Conductive Polymer", technical information about experimental product Polyaniline, Neste Oy, 1995

²⁴R. Strey, G. Porte, P. Bassereau, Langmuir 6, 1635 - 1639 (1990)

M. Kahlweit, R. Strey, G. Busse, J. Phys. Chem. 94, 3881 (1990)

²⁵J. Frommer, R. Elsenbaumer, R. Chance, Org. Coat. Appl. Pol. sci. Proc., 48, 552 (1983)

J. Frommer, Acc. Chem. Res. 19, 2 - 9 (1986)

²⁶A. Andreatta, Y. Cao, J. Chiang, A. Heeger, P. Smith Synthetic Met. 26, 383 - 389 (1988)

²⁷Y. Cao, P. Smith, A. Heeger, Synthetic Met. 57, 3514 (1993)

A. MacDiarmid, A. Epstein, Synthetic Met. 65, 103 - 116 (1994)

²⁸A. Andreatta, Synthetic Met. 41 (3), 1063 (1991); however, from this presentation at the ICSM Göteborg, the author only published the abstract and not the viscosity data presented at the conference

²⁹C. Gettinger, A. Heeger, D. Pine, Y. Cao, Synthetic Met. 74, 81 - 88 (1995)

³⁰because it provides a high shear stress, which is necessary for dispersion, as was shown theoretically [14]

³¹cf. [1], examples 1, 3, 4

³²it should be noted, that the authors mentioned: "In our experiments, we did not observe any measurable effects on the size of the polymer radius until considerably higher water/aniline fractions (about 1000); even at these concentrations the size of the radius was reduced only by a factor of 2." This is in accordance with the consideration, that water is soluble in m-cresol and only a portion is being adsorbed on the PAni particles.

³³Y. Cao, P. Smith, Polymer 34 (15), 3139 - 3143 (1993)

³⁴cf. our theory of the mesoscopic metallic character of polyaniline and ICPs in general: [7]

³⁵R. Cahn, P. Hansen, E. Kramer, eds. "Materials Science and Technology", vol 12; Verlag Chemie 1993

³⁶for more details, B. Wessling, in: R. Elsenbaumer, J. Reynolds, T.Skotheim (eds.) Handbook of Conducting Polymers, Marcel Dekker, in press

³⁷the concentration at which a log(conductivity) vs. concentration plot has its curve inflection point

³⁸from our non-equilibrium theory of dispersion in heterogeneous polymer systems it is understandable, that smaller particles are not possible in polymeric media, as the polymer matrix has to wet the particles being dispersed, which cannot be performed on a surface with such a small radius that, e.g. 10 nm particles would have

³⁹a summary of still actively proposed arguments for this opinion can be found in

- J. Chien, "Polyacetylene", Academic Press 1984

- H. Shirakawa, Y. Zhang, T. Okuda, K. Sakamaki, K. Akagi, Synthetic Met. 65 (2-3), 93 - 102 (1994) and other articles in this issue

⁴⁰I started this debate with publishing the first comparison of a TEM showing fibrillar polyacetylene and a SEM taken from the same sample, showing a globular morphology, cf. B. Wessling, Makromol Chem. 185, 1265 - 1275 (1984)

⁴¹N. Theophilou, D. Swanson, A. MacDiarmid, J. Manotvani, B. Annis, A. Epstein, in: H. Kuzmany, M. Mehring, S. Roth (eds.) "Electronic Properties of Conjugated Polymers III", Springer Series in Solid State Science 91 (1989), 14-18

⁴²Synthetic Metals 65 (2-3) 91 - 262 (1994)

⁴³Y. Liao, K. Kwei, K. Levon, Macromol. Chem. Phys. 196, 3107 - 3116 (1995)

⁴⁴Macromol. Rapid Commun. 16, 393 - 397 (1995)

⁴⁵L. Dai, J. White, J. Polym Sci., B Polym. Phys. 31, 3 - 15 (1993)

⁴⁶SAXS:

⁴⁷P. Garrin, J. Aimé, D. Reibel, C. Mathis, Synthetic Metals 51, 37 - 44 (1992)

⁴⁸SANS:

⁴⁹M. Aldissi, L. Dai, J. Kerr, R. Thomas, J. White, Synthetic Met. 28 (3), D69 (1989)

⁵⁰G. Heffner, D. Pearson, Synthetic Metals 44, 341 - 347 (1991)

⁵¹also R. Elsenbaumer [1] and L. Shacklette [3, and personal communication] always observed "insoluble" portions and precipitates independant from the concentration range they worked in

⁵²which means nothing less than there is no dilution effect resulting in a more complete dissolution, in other words: this is not a true solution, but a nice dispersion!

⁵³which means no more than they had submicron particles - not visible by eye or microscope - responsible for the transparent coloured "solution" and bigger particles which were visible; when the particle size was small enough, than the critical gelation concentration was very low, cf. 5. 1. 3.

⁵⁴tetrabutylammonium-p-toluenesulfonate

⁵⁵R. Gregory, International Conference on Science and Technology of Synthetic Metals 1996, Snowbird (Salt Lake City, US), Synthetic Met. in press

⁵⁶DMPU:

⁵⁷P. Edwards, Acc. Chem. Res. 15, 87 - 93 (1982)

⁵⁸B. Wessling, R. Hiessgen, D. Meissner, Acta Polymer. 44, 132 - 134 (1993)

⁵⁹E. Domalski, E. Hering, J. Phys. Chem. Ref. data 22 (4), 1993, table 2, p. 866ff

⁶⁰ Y. Cao, A. Heeger, Synthetic Met. 52, 193 - 200 (1992)