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1.
W. Haase D. Kilian M. A. Athanassopoulou D. Knawby T. M. Swager S. Wróbel 《Liquid crystals》2013,40(1):133-139
A liquid crystalline vanadyl complex has been studied by DSC, polarizing optical microscopy, the reversal current technique, X-ray diffraction and frequency domain dielectric spectroscopy. The compound exhibits three columnar phases: rectangular ordered (Colro), rectangular disordered (Colrd), and hexagonal disordered (Colhd), all of which show a dielectric relaxation process at low frequencies. In the Colro low temperature phase this process seems to be connected with a slow relaxation of polarized polymeric chains inside the columns (mHz frequency range). However, in the Colhd high temperature disordered phase this relaxation is faster (Hz range). It is interesting that the liquid crystalline phases studied show enhanced conductivity which changes by four orders of magnitude from 10?9 S m?1 in the orientationally disordered crystal (an ODIC phase) to 10?5 S m?1 in the Colhd high temperature phase. Such a value of the conductivity is typical for semiconducting materials. 相似文献
2.
《Liquid crystals》2000,27(4):509-521
Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Colro, Colrd, and Colhd that were identified by X-ray diffraction. In the higher temperature Colrd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Colro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Colro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Colro phase there is an orientationally disordered crystalline Crx phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Crx phase. 相似文献
3.
Robert Forschner Jakob Knelles Korinna Bader Carsten Müller Dr. Wolfgang Frey Prof. Dr. Andreas Köhn Dr. Yann Molard Prof. Dr. Frank Giesselmann Prof. Dr. Sabine Laschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12966-12980
Thermotropic ionic liquid crystals based on the flavylium scaffold have been synthesized and studied for their structure-properties relationship for the first time. The mesogens were probed by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD). Low numbers of alkoxy side chains resulted in smectic (SmA) and lamello-columnar (LamCol) phases, whereas higher substituted flavylium salts showed Colro as well as ordered and disordered columnar (Colho, Colhd) mesophases. Mesophase width ranged from 13 K to 220 K, giving access to room temperature liquid crystals. The optical properties of the synthesized compounds were probed towards absorption and emission properties. Strong absorption with maxima between 444 and 507 nm was observed, and some chromophores were highly emissive with quantum yields up to 99 %. Ultimately, mesogenic and dye properties were examined by temperature-dependent emissive experiments in the solid state. 相似文献
4.
W. Haase D. Kilian M. A. Athanassopoulou D. Knawby T. M. Swager S. Wr bel 《Liquid crystals》2002,29(1):133-139
A liquid crystalline vanadyl complex has been studied by DSC, polarizing optical microscopy, the reversal current technique, X-ray diffraction and frequency domain dielectric spectroscopy. The compound exhibits three columnar phases: rectangular ordered (Colro), rectangular disordered (Colrd), and hexagonal disordered (Colhd), all of which show a dielectric relaxation process at low frequencies. In the Colro low temperature phase this process seems to be connected with a slow relaxation of polarized polymeric chains inside the columns (mHz frequency range). However, in the Colhd high temperature disordered phase this relaxation is faster (Hz range). It is interesting that the liquid crystalline phases studied show enhanced conductivity which changes by four orders of magnitude from 10-9 S m-1 in the orientationally disordered crystal (an ODIC phase) to 10-5 S m-1 in the Colhd high temperature phase. Such a value of the conductivity is typical for semiconducting materials. 相似文献
5.
6.
Dielectric measurements on a sample consisting of banana-shaped molecules were carried out in a frequency range between 0.1 Hz and 10 MHz. The sample exhibited B2 and B4 phases. As usual, two ranges of relaxation were detected in the B2 phase, the fast reorientation about the long axes of the molecules and a slow collective process. In the B4 phase, only one dielectric active process at low frequencies was found; this does not differ from the low frequency relaxation of the B2 modification. This relaxation is probably related to the dynamics of superstructures. Crystallization could be observed after keeping the sample for a longer time at higher temperature. Thus, it was possible to differentiate clearly between the crystalline and the B4 phases. AFM investigations prove the existence of focal-conic domains and periodic superstructures in the B4 phase; then do not appear in the crystalline state. For this reason the B4 phase is regarded as different from a classical crystalline phase. 相似文献
7.
The first clear experimental evidence of a dielectric relaxation in the B7 phase is given. The associated molecular process is probably the reorientation of the bent-shaped molecules about the long molecular axis. It is also shown that the dielectric constant strongly increases at the phase transition I-B7 pointing to a co-operative motion of ferroelectric clusters. Furthermore, a phase transition B7-BX is observed. The values of about 10 for the high frequency limit of the dielectric constants of the B7 and BX phases and the static dielectric constants of the isotropic phase are in agreement. Thus, in all the phases the main dipoles can reorient faster than 10-8 s, i.e. the experimental limit. Only in the supercooled BX phase were the dynamics of the transversal dipoles measured. Using atomic force microscopy, focal-conic domains modulated by parallel lines have been observed at room temperature. 相似文献
8.
The dielectric relaxation behavior of poly(phenylene sulfide), PPS, has been investigated from room temperature to 180°C. This study was undertaken to examine the mobility of the amorphous phase through the glass transition region, to determine the contribution that rigid amorphous phase material makes to the relaxation process. Semicrystalline samples contain a fraction of the rigid amorphous phase, which was determined from the heat capacity increment at the glass transition, using degree of crystallinity determined from x-ray scattering. In the dielectric experiment, we measured the temperature and frequency dependence of the real and imaginary parts of the dielectric function. ε″ vs. ε′ was used to determine the dielectric relaxation intensity, δε = εs–ε∞, at temperatures above the glass transition. For amorphous PPS, δε decreases as temperature increases, while for all semicrystalline PPS, δε increases with temperature. The ratio of semicrystalline intensity to amorphous intensity determines the total fraction of dipoles which are already relaxed at a given temperature. Results indicate that more and more rigid amorphous phase material relaxes as the temperature is increased. This provides the first evidence that rigid amorphous phase material in PPS contains chains that possess different levels of molecular mobility. Finally, to the temperature of the loss peak maximum, at a given frequency, we assign the value of the dielectric Tg. For both melt and cold crystallization, the dielectric Tg systematically decreases as the crystallization temperature increases, and as the fraction of rigid amorphous phase decreases. 相似文献
9.
Abstract : A series of comb-like copolymers and homopolymers containing different liquid-crystalline and perfluoralkyl side chains was studied by frequency and temperature dependent dielectric measurements. The structure and the phase behaviour of the systems were characterized by X-ray scattering and differential scanning calorimetry. The dielectric relaxation spectra of these polymers reflect the molecular mobility in bilayer structures formed by the mesogenic or crystalline side chains. By changing temperature it was possible to investigate the molecular motions in the different phases of the copolymers (smectic-crystalline, smectic-isotropic, and isotropic). The homopolymer containing perfluoralkyl side chains and all copolymers show a β-relaxation at low temperatures, which is assigned to local molecular motions. Above the glass transition temperature, all samples exhibit a segmental (α) relaxation with WLF-like temperature dependence in the activation plots. For the polymers forming LC structures only one relaxation process was detected in all phases, i.e. in the smectic, nematic, and isotropic structure or, in case of the copolymers, in the smectic-crystalline and smectic-isotropic double structures. This process was attributed always to the segmental motions, assisted by tumbling motions of the mesogens. The phase transitions are clearly indicated by discontinuities in the dielectric relaxation times and changes in the relaxation strength Δϵ. The dipole reorientations of the mesogens seem to be more restricted by the crystalline layers in the copolymers as by the smectic order of the LC homopolymers. 相似文献
10.
The phase transition behaviour of three homologous discotic mesogens, the hexa‐n‐alkoxyanthraquinones HOAQ(n), n indicating the number of carbon atoms in the alkoxy group, was investigated under hydrostatic pressures up to 500?MPa using a high pressure differential thermal analyser. The T vs. P phase diagrams of HOAQ(6), HOAQ(8) and HOAQ(9) were constructed for solution‐ (Cr0) and melt‐crystallized (Cr1) samples of the compounds. HOAQ(6) shows the reversible Cr0–rectangular columnar phase (Colr)–hexagonal columnar phase (Colh)–isotropic liquid (I) phase sequence at atmospheric pressure. The stable Colr phase of HOAQ(6) has a decreased temperature range with increasing pressure and then the Colr phase disappears under pressures above about 350?MPa; instead the Cr0–Colh–I phase sequence is exhibited. For HOAQ(8), the solution‐grown sample exhibits the stable Cr0–Colh–I phase sequence at atmospheric pressure. Applying pressure to the solution‐grown sample induces the formation of the stable Colr phase in the pressure region between 10 and 350?MPa, leading to the Cr0–Colr–Colh–I phase sequence. The pressure‐induced Colr phase disappears under higher pressures. The melt‐cooled sample of HOAQ(8) shows the formation of the metastable crystal (Cr1), unknown mesophase (X) and Colr phases at lower temperatures under atmospheric pressure, and exhibits the reversible Cr1–X–Colr–Colh–I phase sequence on subsequent thermal cycles. The metastable phase sequence was observed under pressures up to 100?MPa, but the phase transitions were too small to be detected under higher pressures. In HOAQ(9) the stable Cr0–Colh–I phase sequence is observed at all pressures, while the melt‐cooled sample shows the metastable Cr1–Colr–Colh–I phase sequence under pressures up to 300?MPa. The metastable Colr phase disappears under higher pressures. 相似文献
11.
Charles R. Ashcraft Richard H. Boyd 《Journal of Polymer Science.Polymer Physics》1976,14(12):2153-2193
A study was made of the dielectric relaxation in polyethylenes rendered dielectrically active through oxidation (0.5–1.7 carbonyls/1000 CH2) and chlorination (14–22 Cl/1000 CH2). Both linear and branched polymers were studied. All of the relaxations between the melt and ?196° were studied in the frequency range 10 Hz to 10kHz (100 kHz in the chlorinated samples). In the linear samples a wide range of crystallinities was studied (55% in quenched specimens to 95% in extended-chain specimens obtained by crystallization at 5 kbar). As is consistent with its being a crystalline process, the α peak was found to discontinously disappear on melting of the samples and reappear on recrystallizing on cooling. The disappearance of the smaller crystals before the larger ones appeared to be evident in the isothermal loss versus frequency curves. The relaxation strength of the α process increases with crystallinity. The measured relaxation strength is less than that expected on the basis of direct proportionality to the crystalline fraction with full contribution of all dipoles in the crystalline material. However, the intensity is not sufficiently low for the process to be interpreted in terms of reorientation of localized conformational defects in the crystal. The variation of intensity with crystallinity is best interpreted in terms of full participation of crystalline dipoles but with selective partitioning of both carbonyls and chlorines favoring the amorphous domains. A strong correlation of the α loss peak location (Tmax at constant frequency or log fmax at constant T) with crystallinity for both carbonyl and chlorine containing polymers was found. This variation is interpreted in terms of chain rotations in the crystal where the activation free energy depends on crystal thickness. The dependence of log fmax and Tmax on lamellar thickness as well as a comparison with the loss peaks of ketones dissolved in parafins indicates that the chain rotation is not rigid and is accompanied by twisting as the rotation propagates through the crystal. In agreement with previous studies the β process is found to be strong only in the branched polymers but can be detected in the chlorinated linear polymer. The β process was resolved from the α in the branched samples by curve fitting and its activation parameters determined. The γ relaxation peak in oxidized polymers including its high asymmetry (low-temperature tail) and increasing εmax with increasing frequency and temperature when plotted isochronally can be interpreted in terms of a simple nearly symmetrical relaxation time spectrum that narrows with increasing temperature. No increase in relaxation strength with temperature was found. The chlorinated polymers behave similarly but appear to have some Boltzmann enhancement (450–750 cal/mole) of relaxation strength with temperature. The dependence of relaxation strength on crystallinity indicates that the process is an amorphous one. Further, no evidence of relaxation peak shape changes with crystallinity that could be interpreted in terms of a crystalline component in addition to the amorphous one was found. The comparison of the γ relaxation strength with that expected on the basis of full participation of amorphous dipoles indicates that only a small fraction (~10% in oxidized linear polymers) of them are involved in the relaxation. Thus it would seem that a glass–rubber transition interpretation is not indicated but rather a localized chain motion. It is suggested that the γ process, including its intensity, width, and activation parameters, can be interpreted in terms of an (unspecified) localized conformational (bond rotation) motion that is perturbed by differing local packing environments. The thermal expansion lessens the effects of variations in packing and leads to narrowing with increasing temperature. The conformational motion itself leads to increase in thermal expansion and hence a transition in the latter property. Some previously proposed localized amorphous phase conformational motions appear to be suitable candidates for the bond rotation motion. A weak relaxation peak found at temperatures below the γ and at 10 kHz may possibly be the dielectric analog of the δ cryogenic peak found previously mechanically at lower frequencies. 相似文献
12.
Julius A. Knöller Dr. Robert Forschner Dr. Wolfgang Frey Dr. Johannes Lang Angelika Baro Dr. Anna Zens Prof. Dr. Yann Molard Prof. Dr. Frank Giesselmann Dr. Birgit Claasen Prof. Dr. Sabine Laschat 《Chemphyschem》2022,23(13):e202200154
Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) ( On - Fla - Sm ) as well as thioethers at both A and B ring ( Sn - Fla - Sm ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O1 - iV - Fla - S3 indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O1 - V - Fla - S1 . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and LamCol phases for ILCs with 2–3 chains and Colro, Colh phases for ILCs with 3–6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties. 相似文献
13.
Two polycatenar materials composed of a four‐aromatic‐ring core with a perfluorinated moiety attached in one terminal position through either butylene‐ or pentylene spacer groups, and three tetradecyloxy chains at the other end (abbreviated as 14PC4F and 14PC5F), were investigated to study the effect of pressure on the phase transition behaviour. A polarizing optical microscope equipped with a high pressure optical hot stage, was used for the purpose. The T vs. P phase diagrams of 14PC4F and 14PC5F were constructed in the pressure region up to 100 MPa. 14PC4F showed the stable crystal (Cr1)–columnar tetragonal (Coltet)–smectic A (SmA)–columnar hexagonal (Colh)–isoropic liquid (I) phase transition sequence under all pressures. 14PC5F exhibited the phase sequence metastable crystal (Cr2)–cubic (Cub)–Coltet–SmA–I in a melt‐cooled sample on heating under pressure. But when the melt‐cooled Cr2 sample was annealed at 52–54°C for 2–3 h, the stable crystal (Cr1) was formed slowly, giving a stable Cr1–Cub–Coltet–SmA–I phase sequence. The temperature region of the stable cubic phase broadened with increasing pressure. Furthermore a new mesophase of 14PC5F was pressure‐induced between the I and SmA phases on cooling at pressures above about 16 MPa. Since the monotropic mesophase exhibited a texture very similar to that of the high temperature Colh phase of 14PC4F with planar orientation, the new phase was assigned at a high temperature columnar hexagonal phase of 14PC5F. 相似文献
14.
N. A. Nikonorova N. N. Smirnov G. I. Nosova N. A. Solovskaya A. V. Yakimansky 《Polymer Science Series A》2010,52(12):1301-1310
The molecular mobility of copolymethacrylate with chromophore-containing chalcone side chains is studied by broadband dielectric
spectroscopy. Five regions of dipolar polarization relaxation are identified: namely, γ, β, β1, α, and δ processes. It is shown that γ and β1 processes are related to the local mobility of methylene sequences and ester
groups adjoining the backbone, while the α process is associated with the cooperative segmental mobility of the backbone.
The β and δ processes are attributed to the mobility of chalcone groups: the local mobility in the glassy state (reorientation
relative to the long axis of chromophores) and the cooperative mobility in the rubbery state (reorientation relative to the
short axis of chromophores), respectively. The incorporation of 20% chalcone groups does not change the glass-transition temperature
but enhances the cooperativity of the α process and intermolecular interactions. 相似文献
15.
Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ~10 mum in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength ( Δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC* and SmA) and contributes to the dielectric permittivity. 相似文献
16.
A newly designed anthryl dendron having perfluoroalkyl chains at terminals showed thermotropic liquid crystallinity, which was characterized using polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction. The anthryl dendron forms SB phase at room temperature below 53 °C, at which temperature a phase transition to Colrd takes place. In a fluorous solvent, regioselective photodimerization of the anthryl dendron occurred to give head-to-head photodimers, although photodimerization in the SB phase and chloroform gave both head-to-head and head-to-tail photodimers. 相似文献
17.
Jessie Lorenzo Chao Ilja Grebenchtchikov Robert Kieffer Zinaida Vakhovskaya Ute Baumeister Carsten Tschierske 《Liquid crystals》2013,40(10):1095-1102
In single‐, double‐, and triple‐chain amphiphilic diols the CONH group was replaced by CON(CH3) in order to reduce the number of proton donor groups available for intermolecular hydrogen bonding. The resulting three new liquid crystalline diols were studied by DSC, X‐ray and dielectric measurements, and show the mesophases SmA, ColH2 or CubI2, depending on the number of decyloxy groups in the hydrophobic part of the molecule. The process of self‐assembly to different liquid crystalline phases is well seen in the dielectric spectrum and details of this process are discussed together with results from the X‐ray measurements. All the compounds show a high frequency dielectric absorption caused by the dynamics of the network of hydrogen bonds. An additional low frequency process related to the internal dynamics of the columns is seen only in the columnar phase. 相似文献
18.
A. Durán A.M. Arévalo-López M. García-Guaderrama M.P. Cruz M.A. Alario-Franco 《Journal of solid state chemistry》2010,183(8):1863-1871
Microstructural, magnetothermal and dielectric properties of YCrO3 powders prepared by combustion and solid state methods have been studied by a combination of XRD, specific heat, magnetization and permittivity measurements. The TEM and XRD characterization confirm that the combustion powders are amorphous plate-like agglomerates of nano-sized crystalline particles. A more uniform grain size along with an increase of the relative density is observed by SEM in the sintered samples prepared by combustion route with respect to those produced by solid state reaction. Similar to the material obtained through solid state synthesis, the material prepared by the combustion method also shows spin canted antiferromagnetic ordering of Cr+3 (S=3/2) at ∼140 K, which is shown by magnetization as well as λ-type anomaly in the total specific heat. Furthermore, the magnetic contribution to the total specific heat reveals spin fluctuations above TN and a spin reorientation transition at about 60 K. Both YCrO3 compounds show a diffuse phase transition at about 450 K, typical of a relaxor ferroelectric, which is characterized by a broad peak in the real part of the dielectric permittivity as a function of temperature, with the peak decreasing in magnitude and shifting to higher temperature as the frequency increases. The relaxor dipoles are due to the local non-centrosymmetric structure. Furthermore, the high loss tangent in a broad range of temperature as well as conductivity analysis indicates a hopping mechanism for the electronic conductivity as we believe it is a consequence of the outer d3-shell, which have detrimental effects on the polarization and the pooling process in the YCrO3 bulk material. The more uniform particle size and higher density material synthesized through the combustion process leads to an improvement in the dielectric Properties. 相似文献
19.
Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ~10 μm in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength (δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC% and SmA) and contributes to the dielectric permittivity. 相似文献
20.
Julius Tsuwi Dietmar Appelhans Stefan Zschoche Rong-Chuan Zhuang Peter Friedel Liane Häußler Brigitte Voit Friedrich Kremer 《Colloid and polymer science》2005,283(12):1321-1333
A series of alternating maleimide (MI) copolymers with fluorinated side chains have been investigated using broadband dielectric
spectroscopy. The side chains consist of fluoroalkane (–C
x
F2x+1, x=1, 7, 9) end groups connected to the main chain via methylene spacers. The experiments were carried out in a frequency range
of 0.1 Hz to 10 MHz and at temperatures between 120 K and 500 K. The fluorinated MI copolymers show a fast sub-T
g (β) relaxation characterized by an Arrhenius-type temperature dependence with activation energy in the range of 30–37 kJ/mol.
Two more processes (α and δ-like) are observed, corresponding to independent relaxations of the main chain and the fluoroalkane
domains respectively. For shorter side chains, the δ-like process is not observed but instead another relaxation process,
α
S
, occurs at temperatures higher than either the α and δ-like processes. When compared with unfluorinated MI copolymers, the
fluorinated MI copolymers show the δ-like process and a slower β-relaxation unlike their unfluorinated counterparts. A model
to explain the molecular origin of the four processes is proposed, supplemented by differential scanning calorimetry and published
WAXS/SAXS data. 相似文献