Order-Parameter Temperature Dependences in Nanocomposites of Porous Glass–Sodium Nitrite

Temperature dependences of the order parameter in nanocomposites based on porous borosilicate glasses with mean pore diameters of 20 and 46 nm and filled with sodium nitrite are studied via the diffraction of synchrotron radiation. The mean diffraction sizes of NaNO₂ nanoparticles in the pores of these matrices and the temperatures of the transition of sodium nitrite to the ferroelectric state are determined. It is shown that the phase transition for these nanoparticles remains a first-order phase transition.     

Laser implantation of sodium nitrite into artificial opal pores upon exposure of artificial opal samples to pulsed radiation of the ultraviolet laser

We present experimental results on the introduction (laser implantation) of ferroelectric NaNO₂ into artificial opal pores upon exposure of a thin powder layer of sodium nitrite applied on the artificial opal surface to radiation of the ultraviolet excimer laser. Reflection spectra of broadband radiation from the laser-implanted sample surface are compared with the reflection spectra of pure initial opals, artificial opals impregnated with a saturated aqueous solution of sodium nitrite and evaporated from solvent, and samples in which NaNO₂ was directly introduced in the form of a melt.     

Ferroelectricity in nanocomposites based on porous glass with inclusions of NaNO<Subscript>2</Subscript>

The dielectric nonlinearity and pyroeffect in matrix composite based on porous glass with inclusions of sodium nitrite are investigated. It is found that the composite polarization turns to zero at a temperature below that of the phase transition in the bulk NaNO₂. The obtained dependence of the pyrocoefficient on temperature also corroborates the existence of the phase transition in sodium nitrite nanoparticles included in the porous matrix.     

Specific features in the thermal conductivity of synthetic opals

Data on the thermal conductivity ϰ _ph of the cluster lattice of synthetic opals are analyzed. All opals are divided into two groups according to the temperature dependence of their ϰ _ph. These are opals-1, whose thermal conductivity behaves like ϰ _ph(T) of quasi-crystalline materials, and opals-2, with a ϰ _ph(T) dependence typical of classical amorphous solids. Possible reasons for this difference are considered. An attempt is made to explain the complex temperature hysteresis in ϰ _ph(T) observed earlier in opals-2. Fiz. Tverd. Tela (St. Petersburg) 39, 392–398 (February 1997)     

Acoustic studies of melting and crystallization of sodium nitrite nanocrystals in the pores of mesoporous silicate matrices

A conventional phase-pulse acoustic method was used to study melting and crystallization of sodium nitrite embedded in the pores of mesoporous silicate matrices. The pore diameter was 20, 37, and 52 Å. The measurements were performed at a frequency of 3–8 MHz in the temperature interval 290–560 K. The temperature dependence of ultrasonic velocity was found to exhibit anomalies corresponding to phase transitions of sodium nitrite. The transitions were smeared in temperature and shifted to lower temperatures from the melting point T _b of bulk sodium nitrite; the shift in crystallization temperature was greater than that of the melting temperature. The irreversible character of melting was revealed. The size dependence of the melting temperature of sodium nitrite was obtained. Phenomena observed in the experiments were discussed with the use of different size effect models.     

Laser implantation of sodium nitrite ferroelectric into pores of synthetic opal

We present the experimental results on implantation of NaNO₂ ferroelectric into pores of synthetic opal by illuminating with focused ultraviolet excimer-laser radiation of a sodium nitrite film located on the synthetic-opal surface. The reflection spectra of broadband radiation from the surface of implanted specimens are compared with the reflection spectra of initial (without any treatment) opals, synthetic opals filled with a saturated aqueous solution of sodium nitrite with subsequently evaporated solvent, and specimens with NaNO₂ embedded as a melt. The possible mechanisms of shifts of reflected- and transmitted-radiation peaks are analyzed. Methods of implanting materials with high melting points into pores of 3D photonic crystals are proposed.     

Dielectric and NMR studies of nanoporous matrices loaded with sodium nitrite

NMR and dielectric studies have been performed on NaNO₂ loaded in mesoporous matrices of MCM-41 and SBA-15 with pore sizes of 20, 37, and 52 Å. The spin-lattice relaxation rate and ²³Na NMR line shape, as well as the complex impedance, were measured within a broad temperature interval including the ferroelectric phase transition in bulk NaNO₂. Two different phases of sodium nitrite, the crystalline and melt phases, are shown to coexist under conditions of a restricted geometry. The crystalline phase undergoes a ferroelectric phase transition. The melt fraction increases with temperature. The existence of two phases accounts for all experimental data on NaNO₂ under conditions of a restricted geometry.     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

DSC and elastic moduli studies on tellurite-vanadate glasses containing antimony oxide

xSb₂O₃-40TeO₂-(60 − x) V₂O₅ glasses with 0 ≤ x ≤ 10 (in mol%) have been prepared by rapid- melt quenching method. DSC curves of these ternary glasses have been investigated. The glass transition properties that have been measured and reported in this paper, include the glass transition temperature (T _g ), glass transition width (ΔT _g ), heat capacity change at glass transition (ΔC _P ) and fragility (F). Thermal stability, Poisson’s ratio, fragility and glass forming tendency of these glasses have been estimated, to determine relationship between chemical composition and the thermal stability or to interpret the structure of glass. In addition, Makishima and Makenzie’s theory was applied for determination of Young’s modulus, bulk modulus and shear modulus, indicating a strong relation between elastic properties and structure of glass. Generally, results of this work show that glass with x = 0 has the highest shear, bulk and Young’s moduli which make it as suitable candidate for the manufacture of strong glass fibers in technological applications; but it should be mentioned that glass with x = 8 has higher handling temperature and super resistance against thermal attack.     

Evolution of NaNO<Subscript>2</Subscript> in porous matrices

NMR and dielectric studies of NaNO₂ loaded into an SBA-15 mesoporous matrix are reported. The spin-lattice relaxation rate and the ²³Na NMR line shift, as well as the permittivity, were measured within a broad temperature interval including the ferroelectric phase transition in NaNO₂. The phase transition temperature of sodium nitrite in as-prepared samples was shown to differ substantially from that characteristic of a bulk crystal. The permittivity grows strongly in the vicinity of the phase transition. Heating a sample causes the properties of NaNO₂ embedded in pores to gradually approach those of bulk crystals.     

NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies

In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR), and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k _p/(R−s) with ak _p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek _p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T ₁), spin-spin relaxation times (T ₂), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component at the pore walls and a crystalline solid at the center of the pores. However, theT ₂ measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores. The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T ₁ of the narrow line is significantly shorter thanT ₁ of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of the pore.     

Normal-state electrical resistivity and superconducting magnetic penetration depth in Eu<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript> polycrystals

We report measurements of the temperature dependence of the electrical resistivity, ρ(T), and magnetic pen-etration depth, λ(T), for polycrystalline samples of Eu_0.5K_0.5Fe₂As₂ with T _c = 31 K. ρ(T) follows a linear temperature dependence above T _c and bends over to a weaker temperature dependence around 150 K. The magnetic penetration depth, determined by radio frequency technique displays an unusual minimum around 4 K which is associated with short-range ordering of localized Eu³⁺ moments. The article is published in the original.     

Influence of transport current and thermal fluctuations on the resistive properties of HTSC+CuO composites

Measurements of the temperature dependence of the electrical resistance R(T) below the superconducting transition temperature have been performed at different values of the transport current in HTSC+CuO composites modeling a network of weak S-I-S Josephson junctions (S—superconductor, I—insulator). It has been shown experimentally that the temperature dependence R(T) at different values of the transport current is adequately described by means of the mechanism of thermally activated phase slippage developed by Ambegaokar and Halperin for tunnel structures. Within the framework of this model we have numerically calculated the temperature dependence of the critical current J _c(T) as defined by various criteria. Qualitative agreement obtains between the measured and calculated temperature dependences J _c(T). Fiz. Tverd. Tela (St. Petersburg) 41, 969–974 (June 1999)     

An NMR investigation of naphthalene nanostructures

The molecular mobility of naphthalene molecules in porous silica has been studied over the temperature range 223?K to 363?K using NMR relaxation times T ₂, T ₁ and T _1ρ. The investigations were conducted in silicas with nominal pore diameters of 4?nm, 6?nm, 10?nm, 20?nm and 50?nm. The confined solid behaved in a way that indicated it formed a dual phase system consisting of a solid core in the centre of the pores surrounded by a mobile surface layer. The core naphthalene had the same line width as the bulk. The surface layer exhibited a narrower line of a width that suggested the onset of motional narrowing. This behaviour was characteristic of a plastic crystal phase for naphthalene that does not exist in the bulk. The T ₁ and T _1ρ results were dominated by surface interactions between the confined naphthalene and the pore wall. Magnetization transfer experiments showed that enhanced relaxation occurred throughout the confined material in a time long compared to T ₂ but short compared to T ₁ and T _1ρ. Since the line shape ruled out diffusional motion through the rigid lattice naphthalene core, the magnetization transfer must have occurred via spin diffusion.     

Thermal diffusion near glass transition in Ge-Se glasses measured by photoacoustics

The glass transition in Ge _x Se_1−x ) (0·1 ⩽x ⩽ 0·25) glasses has been investigated using the photoacoustic (PA) technique. It is found that the PA amplitude and phase undergo anomalous changes at the glass transition temperatureT _g. The amplitude has critical minimum and phase has maximum values atT _g. The variation of the thermal diffusivity, determined by measuring the frequency dependence of the PA amplitude and phase, with temperature shows sharp decrease near the glass transition temperature. The temperature dependence of the optical energy gap also has been measured and it shows a decrease with temperature for all compositions, the rate of decrease being higher for temperatures greater thanT _g.     

Size Dependences of the Magnetic Properties of Superconducting Lead–Porous Glass Nanostructures

Superconducting structures Pb–PG formed by filling a porous glass matrix with the lead from melt under pressure have been investigated. Samples with characteristic pore structure diameters of d ≈ 7, 3, and 2 nm have been studied. It has been found that the critical temperature of the superconducting transition in the samples under study is similar to the corresponding value T_c ≈ 7.2 K for bulk lead. At the same time, it has been observed that the critical magnetic field of the nanocomposites, which attains H_c(T = 0 K) ≈ 165 kOe for Pb–PG (3 nm), exceeds several times the value H_c(0) = 803 Oe for bulk lead. The low-temperature magnetic- field dependences of magnetic moment M(H) contain quasi-periodic flux jumps, which vanish with a decrease in the lead nanostructure diameter. A qualitative model of the observed effects is considered.     

Anisotropy of the local field in anisotropic films of conjugated polymers

Using the data on dispersion of refractive indices in the visible region, the experimental values of the components L _j of the Lorentz tensor have been obtained for uniaxial (crystalline, oriented on a substrate, and stretched) films of conjugated polymers from nanometer to micrometer thicknesses. The dependence of the components L _j on the axial and planar orientations of macromolecules with respect to the optical axis of the film, technology of fabricating the films, and chemical structure of macromolecules has been elucidated. The correlation between the components L _j and the measured parameter η has been determined and the analytical dependence L _j (η) for films with both types of macromolecular orientation has been established. In the visible region (0 ≤ η ≤ 0.5), the presence of one point (η = 1/3) of isotropization of the tensor L and three points (η = 0, 1/3, and 0.5) of isotropization of the local field tensor f has been revealed. The point η = 1/3 of isotropization of the tensors L and f has been determined. A comparison has been made between the values of L _j (η) with predictions of known models of the local field for conjugated polymers.     

Suppression of the fractal conductivity channel and superlocalization effects in porous a-Si:H

The temperature dependence of the hopping conductivity and the relaxation kinetics of the transient current in porous amorphous silicon are investigated after treatment in a hydrogen plasma at 200 °C. It is discovered that posthydrogenation of the material increases the dimension of the conducting channel from 2.5 to 3, while suppressing and slowing the relaxation of the transient current. The results obtained are attributed to passivation of the electrically active dangling bonds on the pore surface by hydrogen. It is concluded that electron transport in porous amorphous silicon in the temperature range T>T*, where T* lies in the range 130–270 K and depends on the density of states, takes place between superlocalized states of the internal surface, which is enriched with dangling bonds and acts as a fractal percolation system. When the temperature is lowered below T*, a transition to one-dimensional hopping conduction in the bulk silicon regions occurs. Zh. éksp. Teor. Fiz. 112, 926–935 (September 1997)     

The effect of UV irradiation on temperature dependence of photoluminescence and photoacoustic response in porous silicon

The influence of UV irradiation on temperature dependence of the integral intensity of luminescence I _lum(T) in porous silicon was studied. It was found that, if luminescence decays with temperature nonmonotonically, the peak of I _lum(T) shifts toward higher temperatures as the exciting radiation density increases. Under UV irradiation, the function I _lum(T) becomes monotonically decreasing. If the function I _lum(T) is initially monotonically decreasing, UV preirradiation changes the emission spectrum and accelerates temperature quenching of the red-orange emission band. The variation of the amplitude of the pulsed photoacoustic response with UV irradiation dose was studied. The dependence found is explained by the removal of foreign inclusions from the developed surface of porous silicon. An energy level diagram that makes it possible to explain the behavior of I _lum(T) is suggested. It is noted that the shape of the function I _lum(T) can be used as a test whereby the contributions from dissimilar oscillators to the red-orange emission band are estimated.     

Thermodiffusion of interstitials in a film

A general expression is obtained for the thermodiffusion coefficientD _T of a film, also for its dependence on temperature, film thickness and type of concentration distribution of the interstitials, according to its profile. In neglecting interaction of interstitials with each other in a model of a film with single-plane boundaries with the vacuum and the substrate, it is shown thatD _T>D _T ^(∞) is possible, whereD _T ^(∞) is the thermodiffusion coefficient of a bulk specimen. Ural State Technical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 43–46, September, 1996.