TY - JOUR A1 - Jyotishkumar, P. A1 - Koetz, Joachim A1 - Tiersch, Brigitte A1 - Strehmel, Veronika A1 - oezdilek, Ceren A1 - Moldenaers, Paula A1 - Hässler, Rüdiger A1 - Thomas, Sabu T1 - Complex phase separation in poly(acrylonitrile-butadiene-styrene)-modified epoxy/4,4 '-diaminodiphenyl sulfone blends : generation of new micro- and nanosubstructures N2 - The epoxy system containing diglycidyl ether of bisphenol A and 4,4'-diaminodiphenyl sulfone is modified with poly(acrylonitrile-butadiene-styrene) (ABS) to explore the effects of the ABS content on the phase morphology, mechanism of phase separation, and viscoelastic properties. The amount of ABS in the blends was 5, 10, 15, and 20 parts per hundred of epoxy resin (phr). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were employed to investigate the final morphology of ABS-modified epoxy blends. Scanning electron microscopic studies of 15 phr ABS-modified epoxy blends reveal a bicontinuous structure in which both epoxy and ABS are continuous, with substructures of the ABS phase dispersed in the continuous epoxy phase and substructures of the epoxy phase dispersed in the continuous ABS phase. TEM micrographs of 15 phr ABS-modified epoxy blends confirm the results observed by SEM. TEM micrographs reveal the existence of nanosubstructures of ABS in 20 phr ABS-modified epoxy blends. To the best of our knowledge, to date, nanosubstructures have never been reported in any epoxy/thermoplastic blends. The influence of the concentration of the thermoplastic on the generated morphology as analyzed by SEM and TEM was explained in detail. The evolution and mechanism of phase separation was investigated in detail by optical microscopy (OM) and small-angle laser light scattering (SALLS). At concentrations lower than 10 phr the system phase separates through nucleation and growth (NG). However, at higher concentrations, 15 and 20 phr, the blends phase separate through both NG and spinodal decomposition mechanisms. On the basis of OM and SALLS, we conclude that the phenomenon of complex substructure formation in dynamic asymmetric blends is due to the combined effect of hydrodynamics and viscoelasticity. Additionally, dynamic mechanical analysis was carried out to evaluate the viscoelastic behavior of the cross-linked epoxy/ABS blends. Finally, apparent weight fractions of epoxy and ABS components in epoxy- and ABS-rich phases were evaluated from T-g analysis. Y1 - 2009 UR - http://pubs.acs.org/journal/jpcbfk U6 - https://doi.org/10.1021/Jp8094566 SN - 1520-6106 ER - TY - JOUR A1 - Mondal, Suvendu Sekhar A1 - Mueller, Holger A1 - Junginger, Matthias A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Strehmel, Veronika A1 - Holdt, Hans-Jürgen T1 - Imidazolium 2-substituted 4,5-dicyanoimidazolate ionic liquids: synthesis, crystal structures and structure-thermal property relationships JF - Chemistry - a European journal N2 - Thirty six novel ionic liquids (ILs) with 1-butyl-3-methylimidazolium and 3-methyl-1-octylimidazolium cations paired with 2-substitited 4,5-dicyanoimidazolate anions (substituent at C2=chloro, bromo, methoxy, vinyl, amino, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and phenyl) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and single-crystal X-ray crystallography. The effects of cation and anion type and structure on the thermal properties of the resulting ionic liquids, including several room temperature ionic liquids (RTILs) are examined and discussed. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of -22 to -68 degrees C. The effects of alkyl substituents of the imidazolate anion reflected the crystallization, melting points and thermal decomposition of the ILs. The Coulombic packing force, van der Waals forces and size of the anions can be considered for altering the thermal transitions. Three crystal structures of the ILs were determined and the effects of changes to the cations and anions on the packing of the structure were investigated. KW - crystal structures KW - imidazole KW - ion exchange KW - ionic liquids KW - pi-pi stacking Y1 - 2014 U6 - https://doi.org/10.1002/chem.201304934 SN - 0947-6539 SN - 1521-3765 VL - 20 IS - 26 SP - 8170 EP - 8181 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Sangoro, J. R. A1 - Iacob, C. A1 - Naumov, S. A1 - Valiullin, R. A1 - Rexhausen, Hans A1 - Hunger, J. A1 - Buchner, R. A1 - Strehmel, Veronika A1 - Kaerger, J. A1 - Kremer, F. T1 - Diffusion in ionic liquids the interplay between molecular structure and dynamics JF - Soft matter N2 - Diffusion in a series of ionic liquids is investigated by a combination of Broadband Dielectric Spectroscopy (BDS) and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). It is demonstrated that the mean jump lengths increase with the molecular volumes determined from quantum-chemical calculations. This provides a direct means-via Einstein-Smoluchowski relation-to determine the diffusion coefficient by BDS over more than 8 decades unambiguously and in quantitative agreement with PFG NMR measurements. New possibilities in the study of charge transport and dynamic glass transition in ionic liquids are thus opened. Y1 - 2011 U6 - https://doi.org/10.1039/c0sm01404d SN - 1744-683X VL - 7 IS - 5 SP - 1678 EP - 1681 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Sangoro, Joshia R. A1 - Iacob, C. A1 - Agapov, A. L. A1 - Wang, Yangyang A1 - Berdzinski, Stefan A1 - Rexhausen, Hans A1 - Strehmel, Veronika A1 - Friedrich, C. A1 - Sokolov, A. P. A1 - Kremer, F. T1 - Decoupling of ionic conductivity from structural dynamics in polymerized ionic liquids JF - Soft matter N2 - Charge transport and structural dynamics in low molecular weight and polymerized 1-vinyl-3-pentylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquids (ILs) are investigated by a combination of broadband dielectric spectroscopy, dynamic mechanical spectroscopy and differential scanning calorimetry. While the dc conductivity and fluidity exhibit practically identical temperature dependence for the non-polymerized IL, a significant decoupling of ionic conduction from structural dynamics is observed for the polymerized IL. In addition, the dc conductivity of the polymerized IL exceeds that of its molecular counterpart by four orders of magnitude at their respective calorimetric glass transition temperatures. This is attributed to the unusually high mobility of the anions especially at lower temperatures when the structural dynamics is significantly slowed down. A simple physical explanation of the possible origin of the remarkable decoupling of ionic conductivity from structural dynamics is proposed. Y1 - 2014 U6 - https://doi.org/10.1039/c3sm53202j SN - 1744-683X SN - 1744-6848 VL - 10 IS - 20 SP - 3536 EP - 3540 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Stoesser, Reinhard A1 - Herrmann, Werner A1 - Zehl, Andreas A1 - Strehmel, Veronika A1 - Laschewsky, André T1 - ESR spin probes in ionic liquids N2 - The spin probes 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), and 2,2,6,6-tetramethyl-4-trimethylammoniumpiperidine-1-oxyllodide (CAT-1) are examined in a number of ionic liquids based on substituted imidazolium cations and tetrafluoroborate and hexafluorophosphate anions, respectively. The reorientation correlation times tau(R) of the spin probes in these systems have been determined by complete spectra simulation and, for rapid reortientation, by analysis of the intensities of the hyperfine lines of the electron spin resonance (ESR) spectra. A comparison of the results with those from the model system glycerol/water and selected organic solvents is made. Additions of diamagnetic and paramagnetic ions allow the conclusion that salt effects and spin exchange are present, and that both are superimposed by motional effects. Specific interactions in the ionic liquids, as well as between the spin-probe molecules and the constituents of the ionic liquids are reflected in the spectra of the spin probes, depending on their molecular structure Y1 - 2006 UR - http://onlinelibrary.wiley.com/doi/10.1002/cphc.200500651/full U6 - https://doi.org/10.1002/cphc.200500651 ER - TY - JOUR A1 - Strehmel, Veronika A1 - Berdzinski, Stefan A1 - Rexhausen, Hans T1 - Interactions between ionic liquids and radicals JF - Journal of molecular liquids N2 - Ionic liquids were investigated with both stable radicals on the basis of 2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO) and photogenerated lophyl radicals. The ionic liquids are composed either of bis(trifluoromethylsulfonyl)imide (NTf2) as anion and various cations or they contain an imidazolium ion in combination with various anions. The cations include imidazolium, pyrrolidinium, piperidinium, polymethine or ammonium ions. Furthermore, BF4-, PF6-, triflate, camphorsulfonate, lactate, tosylate or tris(pentafluoroethyl) trifluorophosphate (FAP) are the counter ions in the imidazolium salts. The structural variation of the ionic liquids results in differences in glass formation, semiaystallinity, or crystallinity, as well as in viscosity differences. Furthermore, a vinyl substituent at the imidazolium ion and a methacryloyloxyethyl substituent at the ammonium ion result in polymerizable ionic liquids that were converted via a radical mechanism in amorphous polymerized ionic liquids with a glass transition temperature, which is significantly higher compared to the ionic liquids. An additional substituent at TEMPO causes additional hydrogen bond formation or additional Coulomb interactions with the individual ions of the ionic liquids compared to TEMPO. This influences the mobility of these radicals in the ionic liquid expressed by differences in the average rotational correlation time (T-rot). The mobility of the radicals in the ionic liquids as function of the temperature describes ionic liquids either as continuum in analogy to molecular solvents using the Stokes-Einstein model, that is the case for 1-butyl-3-methylimidazolium NTf2, or as medium where free volume effects are important for the mobility of a solute in the ionic liquid using the model of Spernol, Gierer, and Wirtz. The 1-butyl-3-methylimidazolium BF4- fits well into the latter. Furthermore, the isotropic hyperfine coupling constant (A(iso)(N-14)) of the stable radicals gives information about micropolarity of the ionic liquids only if the mobility of the radical is high enough in the ionic liquid. In addition to the rotational mobility of the stable radicals, the photogenerated lophyl radicals give information about translational diffusion of radicals and solvent cage effects in the ionic liquids. The application of the Eyring equation results mostly in the expected negative values of the activation entropy for the transition state that is typical for bimolecular reactions. Only few examples show a less negative or positive activation entropy for the bimolecular reaction, which may be attributed to radical recombination within the solvent cage to a high extent. The results obtained during investigation of radicals in ionic liquids are important to understand the radical processes in ionic liquids that may occur for example in dye sensitized solar cells, photo or thermally induced reactions or radical polymerizations in ionic liquids. KW - Ionic liquids KW - Radicals KW - Spin probes KW - Polymerized ionic liquids KW - Microviscosity KW - Micropolarity Y1 - 2014 U6 - https://doi.org/10.1016/j.molliq.2013.12.007 SN - 0167-7322 SN - 1873-3166 VL - 192 SP - 153 EP - 170 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Strehmel, Veronika A1 - Berdzinski, Stefan A1 - Strauch, Peter A1 - Hoffmann-Jacobsen, Kerstin A1 - Strehmel, Bernd T1 - Investigation of molecular solvents and ionic liquids with a dual probe JF - Zeitschrift für physikalische Chemie : international journal of research in physical chemistry and chemical physics N2 - A dual probe was investigated by UV-Vis, fluorescence, and ESR spectroscopy. It comprises the pyrene chromophore and the paramagnetic 2,2,6,6-tetramethylpiperidinyl-N-oxyl radical that are covalently linked together via an ester bridge. The dual probe was used to investigate molecular solvents of different polarity as well as ionic liquids bearing either imidazolium or pyrrolidinium cations and various anions, such as bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, tris(pentafluoroethyl)trifluorophosphate, or dicyanamide. The dual probe does not show solvatochromism that is typical for some pyrenes. Furthermore, the dual probe is considerable less mobile compared to 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) without additional substituent as detected by ESR spectroscopy. This is caused by the bulky pyrenyl substituent bound at the dual probe resulting in a reduced mobility of the dual probe. KW - Ionic Liquid KW - Fluorescence KW - ESR KW - Molecular Probe Y1 - 2014 U6 - https://doi.org/10.1515/zpch-2014-0453 SN - 0942-9352 VL - 228 IS - 2-3 SP - 155 EP - 169 PB - De Gruyter CY - Berlin ER - TY - JOUR A1 - Strehmel, Veronika A1 - Kraudelt, Heide A1 - Wetzel, Hendrik A1 - Gornitz, Eckhard A1 - Laschewsky, André T1 - Free radical polymerization of methacrylates in ionic liquids Y1 - 2004 SN - 0065-7727 ER - TY - JOUR A1 - Strehmel, Veronika A1 - Kraudelt, Heide A1 - Wetzel, Hendrik A1 - Görnitz, Eckhard A1 - Laschewsky, André T1 - Free radical polymerization of methacrylates in ionic liquids Y1 - 2004 ER - TY - JOUR A1 - Strehmel, Veronika A1 - Laschewsky, André A1 - Stoesser, Reinhard A1 - Zehl, Andrea A1 - Herrmann, Werner T1 - Mobility of spin probes in ionic liquids N2 - The spin probes TEMPO, TEMPOL, and CAT-1 were used to investigate microviscosity and micropolarity of imidazolium based ionic liquids bearing either tetrafluoroborate or hexafluorophosphate as anions and a variation of the substitution at the imidazolium ion. The average rotational correlation times (r) obtained by complete simulation of the X-band ESR spectra of TEMPO, TEMPOL, and CAT-1 increase with increasing viscosity of the ionic liquid although no Stokes Einstein behavior is observed. This is caused by microviscosity effects of the ionic liquids shown by application of the Gierer-Wirtz theory. Interestingly, the jump of the probe molecule into the free volume of the ionic liquids is a nonactivated process. The hyperfine coupling constants (A(iso) (N-14)) of TEMPO and TEMPOL dissolved in the ionic liquids do not depend on the structure of the ionic liquids. The A(iso) (N-14) values show a micropolarity of the ionic liquids that is comparable with methylenchloride in case of TEMPO and with dimethylsulfoxide in case of TEMPOL. Micropolarity monitored by CAT-1 strongly depends on structural variation of the ionic liquid. CAT-1 dissolved in imidazolium salts substituted with shorter alkyl chains at the nitrogen atom exhibits a micropolarity comparable with dimethylsulfoxide. A significant lower micropolarity is found for imidazolium. salts bearing a longer alkyl substituent at the nitrogen atom or a methyl substituent at C-2. Copyright (c) 2006 John Wiley & Sons, Ltd Y1 - 2006 UR - http://onlinelibrary.wiley.com/doi/10.1002/poc.1072/pdf U6 - https://doi.org/10.1002/poc.1072 ER -