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1.
Using proton NMR relaxometry in the kilohertz frequency range, we study dynamics of 5CB liquid crystal molecules dispersed in the form of spherical microdroplets in a PDLC material. The focus of the study is the spin-lattice relaxation in the rotating frame, T1rho(-1), measured above the nematic-isotropic transition TNI. We show that the relaxation rate T1rho(-1)--when induced by uniform molecular translational diffusion in a spherical cavity--depends on the strength of the rotating magnetic field as T1rho(-1) proportional to omega1(-alpha) where alpha varies between 0.7 and 1, depending on the thickness of the ordered surface layer. This relaxation mechanism governs mainly the transverse spin relaxation, whereas the measurements of the frequency and temperature dependence of T1rho(-1) indicate a strong effect of slowing-down of molecular translational diffusion in contact with the polymer surface and yield the average dwell-time of molecules at the surface of the order 10(-5) s. 相似文献
2.
M. Vilfan N. Vrbančič-Kopač P. Ziherl G. P. Crawford 《Applied magnetic resonance》1999,17(2-3):329-344
We discuss the capability of deuteron nuclear magnetic resonance (NMR) spectroscopy and relaxometry to reveal molecular ordering and dynamics in confined liquid crystals. The attention is focused on the high-temperature phase above the nematic-isotropic transition, which is — in the absence of the long-range orientational order — very suitable for the study of surface interactions. Deuteron NMR spectra and relaxation rates are presented for two representatives of confined liquidcrystal systems: 8CB in cylindrical cavities of Anopore membranes and 5CB with an embedded polymer network. A substantial increase in the transverse spin relaxation rate, stimulated by the surface-induced order in enclosures, has been observed. In cylindrical cavities, it exhibits a strong temperature dependence on approaching the phase transition, whereas in the polymer network dispersion it is temperature-independent. The increase of T 2 ?1 provides information on the effect of spatial constraints on molecular mobility and on the surface orientational order parameter. Using deuteron relaxometry, one can measure the degree of orientational order in the isotropic phase not only in cylindrical but also in spherical cavities and enclosures of irregular shape, where the standard approach based on quadrupolar splitting of the NMR spectrum fails. 相似文献
3.
R. Kausik C. Mattea R. Kimmich N. Fatkullin 《The European physical journal. Special topics》2007,141(1):235-241
Polymer chain dynamics were studied with the aid of
field-cycling NMR relaxometry (time scale: 10-9s...
10-4s) supplemented by field gradient NMR diffusometry
(time scale: 10-4s...100s). Three sorts of samples
of mesoscopically confined polymer melts were examined. In the first
sample series, linear poly(ethylene oxide) was incorporated in
strands embedded in a quasi-solid and impenetrable methacrylate
matrix. The strand diameters ranged from 10 to 60 nm. It was shown
that chain dynamics becomes dramatically different from bulk
behavior. This so-called “corset effect” occurs both above
and below the critical molecular mass and reveals dynamic features
predicted for reptation. On the time scale of spin-lattice
relaxation, the frequency and molecular weight, signature of
reptation, T1 ∼M0 ν3/4, that is limit II of
the Doi/Edwards formalism corresponding to the mean squared segment
displacement law 〈r2 〉∼M0 t1/4, showed
up. A “tube” diameter of only 0.6 nm was concluded to be
effective on this time scale even when the strand diameter was
larger than the radius of gyration of the PEO random coils.
The corset effect is traced back to the lack of the local
fluctuation capacity of the free volume under nanoscopic
confinements. The confinement dimension at which the cross-over from
confined to bulk chain dynamics is expected was estimated to be
micrometers. Using the so-called roll-coating technique, micrometer
thick polymer melt layers between Kapton foils were prepared.
Perceptible differences from the bulk materials were found. The
polymer species studied in this case was perfluoropolyether with
Flory radii in the order of 7 nm. Remarkably, the confinement
effect was shown to reach polymer-wall distances of the order 100
Flory radii. As a third confinement system, melts of
perfluoropolyether were filled into a porous silica glass (Vycor;
4 nm nominal pore size). In this case, a crossover from Rouse
dynamics in the bulk to reptation in the Doi/Edwards limit III
(T1∼M-1/2 ν1/2 corresponding to 〈r2
〉∼M-1/2 t1/2) was observed. 相似文献
4.
Marcos M Cano P Fantazzini P Garavaglia C Gomez S Garrido L 《Magnetic resonance imaging》2006,24(1):89-95
Porous substrates made of poly(3-hydroxybutyrate-3-hydroxyvalerate) (PHBHV) were prepared by a particulate leaching method. After removing the salt by extraction in water, proton nuclear magnetic resonance (NMR) relaxometry and imaging were performed on sets of PHBHV substrates immersed in phosphate-buffered solution during 3 months at different time points. Polarized optical microscopy studies were performed on thin sections, 25 and 5 mum, of the PHBHV samples. The results of NMR relaxometry showed two (1)H nuclei populations, well distinguishable on the free induction decay (FID), due to the different decay time constants, a factor of 10(2) apart. Thus, it was possible to separate the two populations, giving separate distributions of T(1) relaxation times. One population could be associated with water protons in the pores and the other to macromolecular protons. The distributions of T(1) and T(2) of the water proton shifted to lower values with increasing immersion time to a constant value after 30 days. The results obtained by NMR imaging showed an initial increase in the apparent porosity, reaching a plateau after 25 days of immersion. This increase is attributed mainly to the absorption of water in the microporosity as supported by the results of the relaxometry measurements and shown by scanning electron microscopy. The average porosity measured by NMR imaging at the plateau, 78+/-3%, is slightly higher than that determined by optical microscopy, 73+/-9%, which may be due to the fact that the latter method did not resolve the microporosity. Overall, the results suggest that at early stages after immersing the scaffolds in the aqueous medium, first 30 days approximately, NMR imaging could underestimate the porosity of the substrate. 相似文献
5.
6.
L. L. Gur’eva V. P. Tarasov K. V. Ermolaev L. N. Erofeev B. A. Rozenberg 《Applied magnetic resonance》1997,12(4):581-588
Effect of magnetic field on curing a cross-linked polymer based on diglycidyl ester of terephthaloyl-bis (4-hydroxy benzoic acid) in liquid crystalline (LC) state was studied using NMR. The magnetic field was shown to inhibit anionic polymerization. In the course of spontaneous curing the order degree decreased to 0.5 whereas at anionic polymerization the complete disordering was attained. The ordering of the liquid crystalline polymer can be conserved in anionic polymerization if it is performed under controlled temperature conditions. 相似文献
7.
Nilgun Efe Michal Bielejewski Jadwiga Tritt-Goc Behic Mert 《Molecular physics》2019,117(7-8):1034-1045
ABSTRACTSoft candies are popular confectionery products. The most significant concern on the consumption of these products is the high amount of sugar and thus the high calories. The use of low-calorie sweeteners is a desirable trend in confectionery research. In this study, gelatin-based soft candies were formulated by using different sweeteners and their characterisation was performed using high and low field nuclear magnetic resonance (NMR) relaxation experiments. To complement the information obtained by NMR experiments, moisture content, water activity, texture analysis and differential scanning calorimeter experiments were also conducted. T1 and T2 relaxation times were measured at both low and high fields and also temperature-dependent measurements were conducted at the high field system. Candies were formulated by substitution of sucrose with maltitol, isomalt and stevia at 30%, 50% and 70% ratios. Significant difference was observed on relaxation times. T1 values were best described by a mono-exponential model, whereas for T2 relaxation times a bi-exponential model gave better results at both fields. 相似文献
8.
ABSTRACTThe time evolution of the nuclear magnetisation of chemically exchanging systems in liquids is calculated for the pre-polarised fast field-cycling sequence of nuclear magnetic resonance (NMR) relaxometry. The obtained parameter expressions of the magnetisation allow one to derive the longitudinal relaxation rates and the residence times of the exchanging sites from the experiment. In the particular cases of slow and fast exchange, approximations leading to simple analytic expressions are derived. The theory takes account of the delay time necessary to ensure that the field for acquiring the signal is stable enough after its rapid jump from its relaxation value. The domains of mono-exponential or bi-exponential relaxation of the magnetisation are displayed in a concise way through 3D and 2D logarithmic plots of the population ratio of the exchanging sites and of their intrinsic relaxation times. The influence of the acquisition delay on the fitted values of the populations, residence times, and intrinsic relaxation times of the sites is emphasised in the case of the bi-exponential water proton relaxation observed in a tumour tissue. 相似文献
9.
From selective to wide-band light reflection: a simple thermal diffusion in a glassy cholesteric liquid crystal 总被引:1,自引:0,他引:1
M. Mitov A. Boudet P. Sopéna 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,8(3):327-330
Due to their helicoidal structure, cholesteric liquid crystals exhibit remarkable optical properties. Selective light reflection
occurs when the pitch (repeat distance) is of the order of the wavelength of incident light propagating along the helix axis.
The wavelength bandwidth, due to the optical anisotropy, is typically limited to 50 nm which is insufficient for some applications
(full-colors displays, for example). By introducing a pitch gradient in the helix during a novel two-step process in a cholesteric
glass, we show that reflection may occur over a wavelength bandwidth greater than 300 nm. First, the reflection bandwidth
is adjusted by thermal annealing. Then, the optical properties are permanently stored by quenching the viscous material to
a glass at room temperature. The two steps, pitch gradient establishment and film hardening, are independently controlled.
The present process exhibits some reversibility and properties intrinsic to the glassy state are gained: laser-writing high
resolution full-color images on solid films for image recording or high-density optical data-storage are indeed conceivable.
Received 17 December 1998 相似文献
10.
ABSTRACTThe currently available field-cycling NMR relaxometers still suffer from a rather narrow frequency range; they facilitate measurements of the 1H spin–lattice relaxation rate in the frequency of 10?kHz–30?MHz. This limit may be overcome by constructing master curves via exploiting frequency-temperature superposition, the latter being an intrinsic feature of the collective dynamics in many soft matter systems. It states that the shape of the motional time-correlation function is essentially temperature independent over a large temperature interval. As will be demonstrated, master curves may be built in the susceptibility or the spectral density representation of spin–lattice relaxation data. As a result, the effective frequency range is expanded up to ten decades, and the applied shift factors provide the temperature dependence of the corresponding correlation time. Three examples are presented: cyano adamantane in its plastically crystalline phase, the liquid glycerol, and the melt of poly(ethylene propylene). Advantages and limitations of the approach are discussed. 相似文献
11.
12.
The chain dynamics of short-chain perfluoropolyether melts confined in Vycor nanoporous media has been characterized by field cycling nuclear magnetic resonance relaxometry and the dipolar correlation effect. The slowdown of motions under confinement, leading to larger residual dipolar couplings, has been probed by looking at the quotient of stimulated and primary echoes. Using field cycling relaxometry, it has been shown that there is strong evidence of reptation-like motion, even for such short-chain polymers as shown by the frequency and molecular weight dependences of the spin-lattice relaxation time. 相似文献
13.
A.?Van-Quynh P.?J.?Sebasti?o D.?A.?Wilson G.?H.?Mehl 《The European physical journal. E, Soft matter》2010,31(3):275-283
We used proton ( 1H nuclear magnetic relaxation (NMR) dispersions to study the molecular dynamics in the isotropic phase and mesophases (nematic
and columnar hexagonal) of a supermesogenic octapode formed by laterally connecting calamitic mesogens to an inorganic silsesquioxane
cube through flexible spacers. The dispersions of the spin-lattice relaxation time (T1) are interpreted through relaxation mechanisms used for the study of molecular dynamics in low-molar-mass liquid crystals
but adapted to the case of liquid crystalline supermolecules. At high frequencies (above 10MHz) the behaviour of the T1 with the Larmor frequency is similar for all phases and is ascribed to local reorientations and/or rotations. At intermediate
and low frequencies (below 10MHz) our results show notable differences in the T1 behaviour with respect to the mesophases. The nematic (N) and isotropic (Iso) phases’ low-frequency results are similar and
are interpreted for both phases in terms of order director fluctuations (ODF), revealing that even in the isotropic phase
local nematic order is detected by proton NMR relaxometry. Local nematic order in the Iso phase is interpreted in terms of
the presence of nematic cybotactic clusters induced by the interdigitation of mesogens that is promoted by the silsesquioxane
octapode molecular structure. In the columnar hexagonal (Col h phase, the T1 dispersions show that elastic columnar deformations (ECD) dominate the nuclear magnetic relaxation below 10MHz. This result
shows that the columnar packing of the octapode clearly restricts the collective fluctuations of the mesogenic units inspite
of their local nematic order. 相似文献
14.
P. Nozières F. Pistolesi 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,10(4):649-662
We consider a two-dimensional semiconductor with a local attraction among the carriers. We study the ground state of this
system as a function of the semiconductor gap. We find a direct transition from a superconducting to an insulating phase for
no doping at a critical value, the single particle excitations being always gapped. For finite doping we find a smooth crossover.
We calculate the critical temperature due to both the particle excitations and the Berezinkii-Kosterlitz-Thouless transition.
Received 8 December 1998 相似文献
15.
A combined study of2H nuclear magnetic resonance lineshape and spin-lattice and spin-spin relaxation times as functions of temperature and the amount of hydration water in a cross-linked copolymer of sucrose and 1,4-butadienol diglycidyl ether in the hydrogel phase is reported. The results show strong evidence that the onset of the relaxation mechanisms is driven by anomalous water molecule diffusion depending on both temperature and the hydration degree of the hydrogel. In addition, these results are correlated with the transitions observed by differential thermal analysis. 相似文献
16.
C. Bennemann J. Baschnagel W. Paul 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,10(2):323-334
We present simulation results for a model polymer melt, consisting of short, nonentangled chains, in the supercooled state.
The analysis focuses on the monomer dynamics, which is monitored by the incoherent intermediate scattering function. The scattering
function is recorded over six decades in time and for many different wave-vectors which range from the size of a chain to
about three times the maximum position of the static structure factor. The lowest temperatures studied are slightly above
, the critical temperature of mode-coupling theory (MCT), where was determined from a quantitative analysis of the - and -relaxations. We find evidence for the space-time factorization theorem in the -relaxation regime, and for the time-temperature superposition principle in the -regime, if the temperature is not too close to . The wave-vector (q-) dependence of the nonergodicity parameter, of the critical amplitude, and the -relaxation time are in qualitative agreement with calculations for hard spheres. For q larger than the maximum of the structure factor the -relaxation time already agrees fairly well with the asymptotic MCT-prediction . The behavior of the relaxation time at small q can be rationalized by the validity of the Gaussian approximation and the value of the Kohlrausch stretching exponent, as
suggested in neutron-scattering experiments.
Received 30 October 1998 相似文献
17.
We propose a new method to determine wettability indices from NMR relaxometry. The new method uses the sensitivity of low field NMR relaxometry to the fluid distribution in oil-water saturated porous media. The model is based on the existence of a surface relaxivity for both oil and water, allowing the determination of the amount of surface wetted either by oil or by water. The proposed NMR wettability index requires the measurement of relaxation time distribution at four different saturation states. At the irreducible water saturation, we determine the dominant relaxation time of oil in the presence of a small amount of water, and at the oil residual saturation, we determine the dominant relaxation time of water in the presence of a small amount of oil. At 100% water and 100% oil saturation, we determine the surface relaxivity ratio. The interaction of oil with the surface is also evidenced by the comparison of the spin-lattice (T1) and spin-locking (T1rho) relaxation times. The new NMR index agrees with standard wettability measurements based on drainage-imbibition capillary pressure curves (USBM test) in the range [-0.3-1]. 相似文献
18.
NMR relaxometry study of cement hydration in the presence of different oxidic fine fraction materials 总被引:1,自引:0,他引:1
Nestle N 《Solid state nuclear magnetic resonance》2004,25(1-3):80-83
NMR relaxometry has been applied to study hydrating cements for about 25 years now. The most important advantage over other experimental approaches is the possibility to conduct non-destructive measurements with a time resolution of minutes. NMR relaxometry data thus can help to identify details in the time course of cement hydration that possibly would be overlooked in other experiments with lower temporal resolution. Time-resolved information on cement hydration kinetics can provide interesting insights into the impact of oxidic additive materials on cement hydration. For PbO, a very strong delay was observed which then was systematically studied. An explanation for this delay is suggested. 相似文献
19.
Knight shift and spin-lattice relaxation were accurately measured in solid and liquid aluminium from room temperature to 1100°C. The Knight shift in the solid exhibits a strong explicit temperature dependence. K(a), the reciprocal enhancement factor of the Korringa relation, is found to be temperature dependent, an effect which is unaccounted for by the present methods of calculating the susceptibility. 相似文献
20.
《Comptes Rendus Physique》2010,11(2):160-171
A salient characteristic of nuclear magnetic resonance (NMR) techniques is the possibility to scan nuclear spin evolutions within a broad Larmor frequency range. Special instrumentation was developed to extend nuclear spin relaxation studies up to proton Larmor frequencies in the sub-kilohertz regime, a technique known as field-cycling NMR relaxometry. This article refers to an experimental version where the sample under study is selectively subjected to ultrasonic irradiation. The fact that ultrasound couples selectively to the collective dynamics of liquid crystals, offers new insights for the study of the molecular dynamics in these materials using NMR relaxation. 相似文献