Dielectric Spectroscopy of Nematic Liquid Crystal Confined in Random Porous Matrices

1995 ◽  
Vol 411 ◽  
Author(s):  
F. M. Aliev ◽  
G. P. Sinha

ABSTRACTWe performed dielectric spectroscopy measurements to study dynamics of dielectrically active modes of nematic liquid crystals (LC) 5CB with polar molecules confined in silica porous glasses with average pore sizes of 1000 Å (volume fraction of pores 40%) and 100 Å (27%). In the nematic phase of bulk 5CB there is only one mechanism of dielectric relaxation: rotation of polar molecules around short molecular axis with relaxation time τ ∼10−8s. The spatial confinement and the existence of a highly developed interphase have a strong influence on dielectric properties of LC. We found that at temperatures about 30°C below the bulk melting point in both porous matrices the dielectric behavior of confined liquid crystal is very different from the behavior expected for solid state. The dielectric modes were not frozen in both porous matrices and we observed four well defined relaxational processes with relaxation times τ1 ∼ 10−1s, τ2 ∼10−5s, τ3 ∼10−8s (bulk like) and τ3 ∼10−9s. These four processes do not vanish even at temperatures corresponding to deep bulk isotropic phase. The relaxation time of the first process (slow) shows glass-like behavior in a wide temperature range below bulk melting point.

1996 ◽  
Vol 425 ◽  
Author(s):  
F. M. Aliev ◽  
G. P. Sinha

AbstractPorous matrices with determined pore size, volume fraction and structure can be used as model systems to understand physical properties of dispersed liquid crystals (LC) - material important for different applications. Using photon correlation spectroscopy and dielectric spectroscopy we investigated dynamic properties of nematic liquid crystal dispersed in porous matrices with randomly oriented, interconnected pores (porous glasses with average pore sizes of 100 Å and 1000 Å) and parallel cylindrical pores (Anopore membranes with pore diameters of 200 Å and 2000 Å). Since the structural characteristics of these matrices are nearly independent of the temperature, all observable effects due to temperature changes can be attributed to the change in the physical properties of the second component (bC). The spatial confinement and a highly developed interface in porous matrices have a strong influence on the optical and dielectric properties of confined LC which is resulted in: appearance of at least two new dielectrically active modes, absent in the bulk and existence of slow glass-like relaxational process detected in both dielectric and photon correlation experiments.


1994 ◽  
Vol 366 ◽  
Author(s):  
Fouad M. Aliev

ABSTRACTWe performed dielectric spectroscopy measurements to study dynamics of collective modes of ferroelectric (FLC) and molecular motion of nematic (NLC) liquid crystals with polar molecules confined in silica macroporous and microporous glasses with average pore sizes of 1000 Å (volume fraction of pores 40%) and 100 Å (27%) respectively. For FLC the Goldstone and the soft modes are found in macropores. The rotational viscosity associated with the soft mode is about 10 times higher in pores than in the bulk. These modes are not detected in micropores although low frequency relaxation is present. The last one probably is not connected with the nature of liquid crystal but is associated with surface polarization effects typical for two component heterogeneous media. The difference between the dynamics of orientational motion of the polar molecules of NLC in confined geometries and in the bulk is qualitatively determined by the total energy Fs of the interaction between molecules and the surface of the pore wall, which is found Fs ≈ 102erg/cm2.


Nanomaterials ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 1498
Author(s):  
Alexej Bubnov ◽  
Alexey Bobrovsky ◽  
Ivan Rychetský ◽  
Ladislav Fekete ◽  
Věra Hamplová

The control and prediction of soft systems exhibiting self-organization behavior can be realized by different means but still remains a highlighted task. Novel advanced nanocomposite system has been designed by filling of a stretched porous polyethylene (PE) film with pore dimensions of hundreds of nanometers by chiral ferroelectric liquid crystalline (LC) compound possessing polar self-assembling behavior. Lactic acid derivative exhibiting the paraelectric orthogonal smectic A* and the ferroelectric tilted smectic C* phases over a broad temperature range is used as a self-assembling compound. The morphology of nanocomposite film has been checked by Atomic Force Microscopy (AFM). The designed nanocomposite has been studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small and wide-angle X-ray scattering and broadband dielectric spectroscopy. The effect of a porous PE confinement on self-assembling, structural, and dielectric behavior of the chiral LC compound has been established and discussed. While the mesomorphic and structural properties of the nanocomposite are found not to be much influenced in comparison to that of a pure LC compound, the polar properties have been toughly suppressed by the specific confinement. Nevertheless, the electro-optic switching was clearly observed under applied electric field of low frequency (210 V, 19 Hz). The dielectric spectroscopy and X-ray results reveal that the helical structure of the ferroelectric liquid crystal inside the PE matrix is completely unwound, and the molecules are aligned along stretching direction. Obtained results demonstrate possibilities of using stretched porous polyolefins as promising matrices for the design of new nanocomposites.


1995 ◽  
Vol 407 ◽  
Author(s):  
Fouad M. Aliev ◽  
Vladimir V. Nadtotchi

ABSTRACTWe performed dynamic and static light scattering measurements in nematic LC (5CB) confined in silica porous glasses with average pore sizes of 1000 A˚ (volume fraction of pores 40%) and 100 A˚ (27%). The experiments show significant changes in physical properties of confined LC. Nematic-isotropic phase transition temperature TNI is depressed by 0.6°C in 1000 A˚ pores compared to that bulk value and this phase transition was not detected at all in 100 A˚ pores. We found that even about 20°C below bulk melting temperature the relaxational processes in confined LC were not frozen. Slow relaxation process which does not exist in the bulk LC and wide spectrum of relaxation times (10−8 –)s appear in both 100 A˚ and 1000 A˚. In 100 A˚ pores slow relaxation exists even at T corresponding to the bulk isotropic phase. Our data can not be described using the standard form of dynamical scaling variable (t/r) but they obey activated dynamical scaling with the scaling variable x = lnt/lnr.


1997 ◽  
Vol 500 ◽  
Author(s):  
G. P. Sinha ◽  
B. Batalla ◽  
F. M. Aliev

ABSTRACTWe applied ultra broad-band dielectric spectroscopy in the frequency range from 10–3 Hz to 109 Hz to investigate the effect of size, shape and volume fraction of the pores in the porous matrices on the dielectric properties of liquid crystals (LC) dispersed in these matrices. Measurements in such a broad frequency range make it possible to obtain detailed information on the important aspects of the electrical behavior of heterogeneous materials such as: conductivity, surface polarization, and influence of confinement on dynamics of molecular motion of polar molecules forming LC. We investigated alkylcyanobiphenyls in the isotropie, nematic and smectic phases dispersed in porous glasses (average pore sizes - 100 Å and 1000 Å) which have randomly oriented, interconnected pores, and anopore membranes (pore diameters - 200 Å and 2000 Å) with parallel cylindrical pores. Dispersion of LC resulted in qualitative changes of their dielectric properties. Analysis of broad-band dielectric spectra shows that in organic (LC) - inorganic (porous matrix) heterogeneous composites conductivity plays an important role at F <1 Hz. We observe the appearance of new dielectric modes: a very slow process with characteristic frequency ≃ (1 – 10) Hz and a second process in frequency range about (103 - 106) Hz. The slow process arises due to the relaxation of interfacial polarization at pore wall - LC interface. The origin of this could be due to absorption of ions at the interface. Another possibility is the preferential orientation of the permanent dipoles at pore surface. The second new mode is due to the hindered rotation of the molecules near the interface. Additionally we observed two bulk like modes due to the rotation of the molecules around their short and long axii which are modified.


1974 ◽  
Vol 52 (14) ◽  
pp. 1331-1335 ◽  
Author(s):  
Ronald Y. Dong ◽  
M. Wiszniewska ◽  
E. Tomchuk ◽  
E. Bock

The proton spin-lattice relaxation time T1 in the isotropic phase of the smectic A liquid crystal diethylazoxybenzoate was measured at several Larmor frequencies in the range from 5 to 60 MHz. The frequency dependent T1 at 25 °C above the smectic A-isotropic phase transition (Tc) is attributed to molecular diffusion. The critical temperature dependent (T1)cf, the spin-lattice relaxation time due to critical order fluctuations, at 5 MHz can be understood by assuming that the effective viscosity has a critical temperature behavior just above Tc. It was deduced that the effective viscosity diverges as ξ2 in the mean field approximation, where ξ is a coherence length describing the short range order.


2017 ◽  
Vol 54 (3) ◽  
pp. 181-201
Author(s):  
Rebecca Johnson ◽  
Mark Longman ◽  
Brian Ruskin

The Three Forks Formation, which is about 230 ft thick along the southern Nesson Anticline (McKenzie County, ND), has four “benches” with distinct petrographic and petrophysical characteristics that impact reservoir quality. These relatively clean benches are separated by slightly more illitic (higher gamma-ray) intervals that range in thickness from 10 to 20 ft. Here we compare pore sizes observed in scanning electron microscope (SEM) images of the benches to the total porosity calculated from binned precession decay times from a suite of 13 nuclear magnetic resonance (NMR) logs in the study area as well as the logarithmic mean of the relaxation decay time (T2 Log Mean) from these NMR logs. The results show that the NMR log is a valid tool for quantifying pore sizes and pore size distributions in the Three Forks Formation and that the T2 Log Mean can be correlated to a range of pore sizes within each bench of the Three Forks Formation. The first (shallowest) bench of the Three Forks is about 35 ft thick and consists of tan to green silty and shaly laminated dolomite mudstones. It has good reservoir characteristics in part because it was affected by organic acids and received the highest oil charge from the overlying lower Bakken black shale source rocks. The 13 NMR logs from the study area show that it has an average of 7.5% total porosity (compared to 8% measured core porosity), and ranges from 5% to 10%. SEM study shows that both intercrystalline pores and secondary moldic pores formed by selective partial dissolution of some grains are present. The intercrystalline pores are typically triangular and occur between euhedral dolomite rhombs that range in size from 10 to 20 microns. The dolomite crystals have distinct iron-rich (ferroan) rims. Many of the intercrystalline pores are partly filled with fibrous authigenic illite, but overall pore size typically ranges from 1 to 5 microns. As expected, the first bench has the highest oil saturations in the Three Forks Formation, averaging 50% with a range from 30% to 70%. The second bench is also about 35 ft thick and consists of silty and shaly dolomite mudstones and rip-up clast breccias with euhedral dolomite crystals that range in size from 10 to 25 microns. Its color is quite variable, ranging from green to tan to red. The reservoir quality of the second bench data set appears to change based on proximity to the Nesson anticline. In the wells off the southeast flank of the Nesson anticline, the water saturation averages 75%, ranging from 64% to 91%. On the crest of the Nesson anticline, the water saturation averages 55%, ranging from 40% to 70%. NMR porosity is consistent across the entire area of interest - averaging 7.3% and ranging from 5% to 9%. Porosity observed from samples collected on the southeast flank of the Nesson Anticline is mainly as intercrystalline pores that have been extensively filled with chlorite clay platelets. In the water saturated southeastern Nesson Anticline, this bench contains few or no secondary pores and the iron-rich rims on the dolomite crystals are less developed than those in the first bench. The chlorite platelets in the intercrystalline pores reduce average pore size to 500 to 800 nanometers. The third bench is about 55 ft thick and is the most calcareous of the Three Forks benches with 20 to 40% calcite and a proportionate reduction in dolomite content near its top. It is also quite silty and shaly with a distinct reddish color. Its dolomite crystals are 20 to 50 microns in size and partly abraded and dissolved. Ferroan dolomite rims are absent. This interval averages 7.1% porosity and ranges from 5% to 9%, but the pores average just 200 nanometers in size and occur mainly as microinterparticle pores between illite flakes in intracrystalline pores in the dolomite crystals. This interval has little or no oil saturation on the southern Nesson Anticline. Unlike other porosity tools, the NMR tool is a lithology independent measurement. The alignment of hydrogen nuclei to the applied magnetic field and the subsequent return to incoherence are described by two decay time constants, longitudinal relaxation time (T1) and transverse relaxation time (T2). T2 is essentially the rate at which hydrogen nuclei lose alignment to the external magnetic field. The logarithmic mean of T2 (T2 Log Mean) has been correlated to pore-size distribution. In this study, we show that the assumption that T2 Log Mean can be used as a proxy for pore-size distribution changes is valid in the Three Forks Formation. While the NMR total porosity from T2 remains relatively consistent in the three benches of the Three Forks, there are significant changes in the T2 Log Mean from bench to bench. There is a positive correlation between changes in T2 Log Mean and average pore size measured on SEM samples. Study of a “type” well, QEP’s Ernie 7-2-11 BHD (Sec. 11, T149N, R95W, McKenzie County), shows that the 1- to 5-micron pores in the first bench have a T2 Log Mean relaxation time of 10.2 msec, whereas the 500- to 800-nanometer pores in the chlorite-filled intercrystalline pores in the second bench have a T2 Log Mean of 4.96 msec. This compares with a T2 Log Mean of 2.86 msec in 3rd bench where pores average just 200 nanometers in size. These data suggest that the NMR log is a useful tool for quantifying average pore size in the various benches of the Three Forks Formation.


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