TY - JOUR A1 - Freydank, Anke-Christine A1 - Janietz, Silvia A1 - Schulz, Burkhard T1 - Synthesis and electrochemical characterization of new amphiphilic 1,3,4-oxadiazoles N2 - The electrochemical behaviour of new amphiphilic 1,3,4-oxadiazoles were studied by cyclic voltammetry. The influence of the supra- molecular structure on the redox behaviour in liquid or solid solutions, in Langmuir-Blodgett multilayers, and in amorphous films is investigated in detail. The reversible reduction of amphiphilic 2,5-diarylene- 1,3,4-oxadiazoles is significantly influenced by substituents in the para position of the phenylene ring. In the solid states the reduction peak potentials are shifted to more negative values compared to data measured in solution. This shift increases as the film thickness is increased. An influence of the supramolecular order in the solid films was not found. In-situ UV-vis spectroelectrochemistry of LB-multilayers deposited onto indium tin oxide (ITO) glass give evidence for the formation of radical anions in the highly ordered layer. Y1 - 1998 ER - TY - JOUR A1 - Lavrenko, Peter N. A1 - Okatova, Olga V. A1 - Schulz, Burkhard T1 - Stability and degradation of poly(p-pheneylene-1,3,4-oxadiazole) molecules in sulphuric acid N2 - The translational diffusion coefficient and intrinsic viscosity of poly(1,4-phenylene-1,3,4-oxadiazole) molecules in 96% H2S04 have been determined at different stages of degradation of the molecules in acid solution at temperature ranging from 82 to 105 °C. The degradation rate constant, k, has been obtained from the change in the molecular weight, M, of the product degraded in solution with time at high temperature. The activation energy of the hydrolysis process was 103 ± 7 kJmol-1, which is smaller than that of aromatic polyamides in the same solvent. According to our hydrodynamic data, the degree of coiling of the molecules of degraded products does not differ from that of undegraded samples, and our conclusion was that the degradation is not accompanied with a noticeable change in the short- range interactions in the molecular chain and may be understood as a random chain scission. Y1 - 1998 ER - TY - JOUR A1 - Lavrenko, Peter N. A1 - Okatova, Olga V. A1 - Schulz, Burkhard T1 - Hydrodynamic properties and conformation of the molecules of meta- and para-isomers of polyphenyleneoxadiazole in sulphuric acid N2 - Translational diffusion of poly(1,4-phenylene-1,3,4-oxadiazole) in 96% H2S04 was studied, and the intrinsic viscosity of the polymer solution was measured in various stages of degradation at temperatures from 82 to 105°C. The rate constant of the degradation process was determined from variation of the molecular mass of the degradation products with time at a fixed solution temperature, and the activation energy of the process was calculated using the temperature dependence of the rate constant. The activation energy (E = 103 ± 7 kJ/mol) is lower than that for the hydrolysis of aromatic polyamides in sulfuric acid. According to the hydrodynamic data, the degree of coiling of the degradation products is the saine as that of the intact (non-degraded) macromolecules. This indicates that elements of the chernical structure responsible for the short-range order in the macromolecular chain are retained in the course of degradation. Y1 - 1998 ER - TY - JOUR A1 - Bruma, Maria A1 - Sava, Ion A1 - Mercer, Frank W. A1 - Reddy, Victor N. A1 - Köpnick, Thomas A1 - Stiller, Burkhard A1 - Schulz, Burkhard T1 - Silicon-containing poly(amide-ether)s N2 - New aromatic poly(amide-ether)s (II) have been synthesized by solution polycondensation of various aromatic diamines having two ether bridges (I) with a diacid chloride containing silicon, namely bis(chlorocarbonylphenyl)- diphenyIsilane. These polymers are easy soluble in polar amidic solvents such as N-methylpyrrolidinone or dimethylformamide and can be cast into thin flexible films or coatings from such solutions. They show high thermal stability with initial decomposition temperature being above 400 °C. Their glass transition temperatures lie in the range of 220-250 °C, except for polymer He which did not show a clear Tg when heated in a differential scanning calorimetry experiment up to 300 °C. The large interval between the glass transition and decomposition temperatures of pnlymers Ia-Id could be advantageous for their processing via compression molding. The polymer coatings deposited by the spincoating, technique onto silicon wafers showed a very smooth, pinhole-free surface in atomic force microscopy investigations. The free-standing films of 20-30 mm thickness show low dielectric constant, in the range of 3.65-3.78, which is promising for future application as high performance dielectrics. Y1 - 1998 ER - TY - JOUR A1 - Bruma, Maria A1 - Schulz, Burkhard A1 - Köpnick, Thomas A1 - Dietel, Reinhard A1 - Stiller, Burkhard A1 - Mercer, Frank W. T1 - Investigation of thin films made from silicon-containing poly(phenylquinoxaline-amide)s N2 - Thin films in the range of 50 nm to 10 mm thickness have been prepared from NMP solutions of silicon-containing polyphenylquinoxaline-amides which had been synthesized by the polycondensation reaction of aromatic diaminophenylquinoxalines with bis(p-chlorocarbonylphenyl)diphenylsilane. A spin-coating technique onto glass plates or onto silicon wafers was used to make the film, followed by gradual heating to remove the solvent. The resulting films were very smooth and free of pinholes when studied by atomic force microscopy (AFM). They showed a strong adhesion to silicon wafers, were thermally stable in air to above 400 °C and their dielectric constant was in the range of 3.5-3.7. Thermal treatment of the films was performed in order to induce crosslinking. Such treated films became completely insoluble in organic solvents, maintained their smoothness and strong adhesion to the silicon substrate, and did not show any Tg, in DSC experiments. Their FTIR spectra in reflection mode did not show any changes compared with the untreated films, meaning on the one hand that the polymers maintain their structural integrity at high temperature and on the other hand that the number of crosslinks was very low and could not be detected by IR spectroscopy. Y1 - 1998 ER - TY - JOUR A1 - Lavrenko, Peter N. A1 - Okatova, Olga V. A1 - Cherkasov, Victor A. A1 - Schulz, Burkhard T1 - Hydrodynamic properties of Poly(p-phenylene-oxadiazole) in various stages of hydrolytic thermal degradation in sulfuric acid Y1 - 1998 ER - TY - JOUR A1 - Orgzall, Ingo A1 - Lorenz, Bernd A1 - Mikat, Jürgen E. R. A1 - Reck, Günter A1 - Knochenhauer, Gerald A1 - Schulz, Burkhard T1 - Phase transition in 1,3,4-oxadiazole crystals under high pressure Y1 - 1998 ER - TY - JOUR A1 - Bruma, Maria A1 - Schulz, Burkhard A1 - Köpnick, Thomas A1 - Stiller, Burkhard A1 - Hamciuc, Elena A1 - Mercer, Frank W. A1 - Cassidy, Peter T1 - Aromatic polyamides with hexafluoroisopropylidene groups and study of the thin Y1 - 1998 ER - TY - JOUR A1 - Bruma, Maria A1 - Schulz, Burkhard A1 - Köpnick, Thomas A1 - Stiller, Burkhard A1 - Belomoina, Nataliya A1 - Mercer, Frank W. T1 - Synthesis and study of aromatic polyamides containing silicon and phenylquinoxaline rings in the main chain N2 - New poly(phenylquinoxaline-amide)s with silicon in the main chain have been prepared by polycondensation reaction of a diacid chloride, namely bis(p-chlorocarbonyl-phenyl)-diphenylsilane, with aromatic diamines containing one or two phenylquinoxaline rings separated by a flexible bridge such as ether or methylene. These polymers were easily soluble in polar aprotic solvents such as N-methylpyrrolidinone (NMP) and dimethylformamide (DMF) and showed high thermal stability with decomposition temperature being above 450°C and glass transition temperature in the range of 260- 304°C. Polymer solutions in NMP were processed into thin flexible films which exhibited very smooth surfaces, free of pinholes when studied by atomic force microscopy. The free-standing films showed a dielectric constant in the range of 3.6-3.7. Y1 - 1999 ER - TY - JOUR A1 - Bruma, Maria A1 - Hamciuc, Elena A1 - Schulz, Burkhard A1 - Köpnick, Thomas A1 - Stiller, Burkhard A1 - Mercer, Frank W. T1 - Synthesis of fluorinated poly(phenylquinoxaline-amide)s and study of thin films made therefrom N2 - A series of five fluorinated poly(phenylquinoxaline-amide)s were synthesized by a polycondensation reaction of a diacid chloride containing the hexafluoroisopropylidene (6F) group, namely 2,2-bis(p-chlorocarbonylphenyl)- hexafluoropropane, with various aromatic diamines incorporating two phenyl-substituted quinoxaline rings. These polymers were easily soluble in polar aprotic solvents such as N-methylpyrrolione (NMP), dimethylformamide (DMF), and tetrahydrofurane (THF), and showed a high thermal stability with decomposition temperatures above 400 °C and glass transition temperatures in the range of 260-290 Tg. Polymer solutions in NMP were processed into free-standing films that showed low dielectric constant values, in the range of 3.4-3.9, and good mechanical properties, with tensile strength in the range of 40-80 MPa and elongation to break in the range of 22-55%. Very thin films, in the range of tens of nanometer, which were deposited onto silicon wafers exhibited very smooth surfaces, free of pinholes when studied by atomic force microscopy (AFM). Y1 - 1999 ER -