MAS NMR studies of nanoporous matrices filled with sodium nitrite

The sodium nitrite NaNO2 incorporated into MCM-41 molecular sieves with pore sizes of 20, 26, and 37 Å has been investigated by 23Na magic-angle spinning NMR spectroscopy. It has been demonstrated that the structure of the crystalline phase of the nitrite in a confined geometry is similar to the structure of bulk nitrite NaNO2. The direct proof of the diffuse melting of sodium nitrite in the pores has been obtained. The NMR signal of the molten sodium nitrite phase has been observed at temperatures close to the completion of the melting.     

Studies of nanoporous matrices filled with sodium nitrite by nonlinear dielectric spectroscopy

Variation of nanocrystalline NaNO₂ properties was studied under the conditions of confined geometry by nonlinear dielectric spectroscopy. It was shown that a decrease in the pore size of silicate matrices MCM-41 filled with NaNO₂ leads to an increase of nonlinearity and a change in the shape of the curves of the third harmonic amplitude as a function of temperature.     

Dielectric studies of nanoporous alumina films filled with the Rochelle salt

Dielectric studies of nanoparticles of the Rochelle salt embedded in pores of porous alumina have been performed in the temperature range from 80 K to the decomposition temperature of the bulk Rochelle salt. It has been revealed that the permittivity exhibits an anomaly corresponding to the lower structural transition to the paraelectric phase, whereas the upper ferroelectric transition is shifted above the decomposition temperature in agreement with the recently published data. The temperature of the lower transition for nanoparticles in pores is found to decrease by 10 K. Possible physical factors that can be responsible for the broadening of the region of existence of the ferroelectric phase have been discussed.     

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.     

Dielectric properties of mixed NaNO2-KNO3 ferroelectrics in nanoporous silicate matrices

Physics of the Solid State - Results of dielectric studies of MCM-41 molecular sieves with mesoporous channels (37.0 and 24.3 Å in size) loaded with the ferroelectric (NaNO2)1 ? x (KNO3)...     

Secondary radiation of synthetic opals loaded by the sodium nitrite ferroelectric

This paper reports on a comparison of transmission, reflection, and secondary radiation spectra of unloaded synthetic opals and samples filled with the sodium nitrite ferroelectric (NaNO₂). The radiation is provided by semiconductor light-emitting diodes operating in the ultraviolet and visible spectral regions. Selective excitation of slow electromagnetic waves in a photonic crystal, an effect observed when the exciting radiation frequency approaches the stop-band edge, is studied.     

Dielectric and calorimetric investigations of KNO3 in pores of nanoporous silica matrices MCM-41

The temperature dependences of the linear dielectric permittivity, the third harmonic amplitude, and the heat capacity of nanoporous silica matrices MCM-41 with cellular channels (3.7 and 2.6 nm in diameter) filled with KNO₃ have been investigated in comparison with those obtained for bulk potassium nitrate. Measurements have been performed during heating and cooling in the range from room temperature to 463 K. Anomalies corresponding to structural phase transitions have been observed. A significant broadening of the temperature region of the existence of the ferroelectric phase III of potassium nitrate upon cooling has been revealed. This broadening increases with a decrease in the size of pores. It has been shown that, in the nanocomposites with potassium nitrate, the ferroelectric phase can also be formed during heating. The efficiency of observation of the third harmonic generation for studying nanocomposites with the ferroelectric phase has been demonstrated.     

Dielectric and elastic responses of nanostructured sodium nitrite in a porous glass

The dielectric and elastic properties of the SiO₂-NaNO₂ nanocomposite obtained by incorporation of sodium nitrite into a porous glass matrix with an average pore diameter of ≈7 nm have been investigated in the temperature range 300–550 K. A significant softening of the shear modulus has been revealed in the temperature range 380–520 K, which corresponds to the premelting region of the embedded material. Analysis of the dielectric response spectra at frequencies from 1 Hz to 2.5 MHz has revealed four relaxation processes, two of which are thermally activated. The nature of the relaxation processes is discussed.     

Dielectric and NMR Studies of the superionic conductor AgI embedded in mesoporous silicate matrices

This paper reports on the results of studies of small particles of the superionic conductor AgI embedded in MCM-41 and SBA-15 molecular sieves with different sizes of pores (channels). The studies are performed by the dielectric and nuclear magnetic resonance techniques. The temperature of the superionic phase transition is shown to increase monotonically with decreasing pore size. The enthalpy of activation of the ion motion in β-AgI in restricted geometry is determined. It is shown that introduction of AgI into pores does not noticeably affect its structure.     

NMR property of sodalite loaded with potassium

²⁷Al NMR property of potassium-loaded sodalite, which shows antiferromagnetic transition around 70 K, is reported. Monotonic narrow spectrum above 70 K is broadened below 70 K. The broadened spectrum is analyzed with an assumption that the broadening is given by dipolar field from magnetic moment in the cage of sodalite. Two Gaussian functions are used for fitting. Widths of each component proportionally scale each other. The ratio between the Gaussian widths of each component of the narrower and the broader components is 15±3.     

Dielectric relaxation studies of alkanols solubilized by sodium dodecyl sulphate aqueous solutions

Considerable attention has been paid in recent years to the influence of alcohols on ionic micellar structures, alcohol co-surfactants most commonly employed in the preparation of microemulsions. Dielectric relaxation spectroscopy (DRS) is a versatile tool to monitor the dynamic process of such micellar systems. We report here the changes in the dielectric constant of the medium and the relaxation time of micellar solutions of sodium dodecyl sulphate (SDS) in water in the presence and absence of alkanols—hexan-1-ol, octan-l-ol, decan-l-ol and 1,2-ethanediol. The time domain dielectric data were obtained in the reflection mode in the frequency range of 10 MHz to 20 GHz using a HP54750A sampling oscilloscope and HP 54754A TDR plug-in-module. The sample is held at 303 K in a SMA cell with an effective pin length of 1.35 mm. We have determined the relaxation time (τ) using the Cole–Cole method. The relative viscosity ηr on the micellar solutions were also determined. The result shows that the dielectric constant increases linearly with SDS concentration in pure aqueous solutions up to 400 mM and decreases thereafter. The relaxation times are of the order of 15 ps to 25 ps and are far greater than that of Debye rotational relaxation of the monomer species. It is assigned to the dispersion step to water molecules surrounding to hydrophobic particles or the “bound water”. The addition of alcohols results in a linear increase in relaxation time in all the systems. As the concentration of SDS increases τ/ηr attains a near constant value showing that solubilization becomes more difficult at these concentrations. Our results show that the alcohol molecules are solubilized at the surface of the SDS micelle (i.e.) the micelle–water interface.     

Structure and properties of confined sodium nitrite

We study the lateral and transverse diffusion of amphiphiles in two-component bilayer membranes, using a coarse-grained model for amphiphilic molecules and combined Monte Carlo-Molecular Dynamics simulations. Membrane structural properties, such as the mean thickness, are also measured. The dependence of such properties on membrane composition, inter-molecular interactions, and amphiphile stiffness is determined. In particular, we show that addition of shorter amphiphiles drives the model membrane towards a more fluid state, with increased amphiphile lateral diffusion rates. These results can be understood in the framework of a simple free-volume model. Furthermore, we observe an increase in the trans-membrane diffusion when the interaction energy of amphiphiles with their neighboring molecules is decreased. Received: 6 December 2002 / Accepted: 17 April 2003 / Published online: 27 May 2003 RID="a" ID="a"e-mail: imparato@mpikg-golm.mpg.de RID="b" ID="b"e-mail: shillcock@mpikg-golm.mpg.de RID="c" ID="c"e-mail: lipowsky@mpikg-golm.mpg.de     

Structure and properties of confined sodium nitrite

The temperature evolution of the structure of NaNO(2) nanocomposite ferroelectric material in a porous glass with 7 nm pores was studied by neutron diffraction in temperature region from room temperature up to the melting, i.e. in the ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with the structure of the bulk, but above the ferroelectric phase transition (and up to approximately 513 K) a volume premelted state is formed, manifesting itself in a growth of amplitudes of ion thermal vibrations, a steep increase of elementary cell volume and "softening" of lattice. For the first time the temperature dependence of order parameter eta for confined sodium nitrite is determined. eta (T) follows a power law with T(C)=425.6+/- 2.1 K and beta= 0.31+/- 0.04, which is essentially different from that for bulk NaNO(2). Our obtained data are in a good agreement with the results of earlier dielectric and neutron diffraction measurements.     

Combined 17O NMR and 11B-31P double resonance NMR studies of sodium borophosphate glasses

17O enriched sodium borophosphate glasses were prepared from isotopically enriched NaPO3 and H3BO3. These glasses have been studied by 17O, 11B and 31P NMR including 17O and 11B multiple quantum magic angle sample spinning (MQMAS), 11B-31P heteronuclear correlation (HETCOR) NMR and 11B{31P} rotational echo double resonance (REDOR). For comparison, the crystalline borophosphates BPO4 and Na5B2P3O13 were included in the investigations. The latter compound shows three sharp 31P resonances at -0.2, -2 and -8 ppm and two BO4 sites that can only be resolved by MQMAS. The 17O NMR spectra were recorded using both the static echo method at medium magnetic field (9.4 T) as well as MAS and MQMAS methods at high field (17.6 T). In total, five oxygen sites were identified in these borophosphate glasses: P-O-P, Na...O-P, P-O-B, B-O-B, Na...O-B. However, these five sites are not present simultaneously in any of the glasses. The 17O MQMAS spectra prove that P-O-B links play a major role in borophosphate glasses. These results are confirmed by the complementary 11B MAS spectra that show the presence of asymmetric and symmetric trigonal groups BO3a and BO3s and two tetrahedral BO4 units. 11B{31P} REDOR NMR is used to give independent information to assign the 11B lines to structural units present in the glasses. These REDOR measurements reveal that B-O-P bonds are present for each borate unit, including the BO3 groups. Particularly, a structural proposal for the two different BO4 resonances is given in terms of a different number of bonded phosphate tetrahedra. The 31P MAS spectra are usually broad and not well resolved. It is shown by 11B-31P HETCOR NMR that a possible structural assignment of a 31P signal at about -20 ppm to Q2 units as in binary sodium phosphate glasses is wrong and that the phosphate tetrahedron belonging to this resonance must be connected to borate groups.     

Multinuclear NMR studies on the sol-gel preparation of sodium aluminophosphate glasses

Sodium aluminophosphate gels and glasses in the system NaPO₃–Al₂O₃ with P/Al ratios ranging from 9:1 to 1:1 have been synthesized by a novel sol–gel route based on the reaction of aluminum lactate with sodium polyphosphate in aqueous solution. The route from the solution to the gel and the final glass was monitored in situ by liquid and solid state NMR techniques, characterizing the influence of composition and pH on the hydrolysis, polymerization, and vitrification processes. The site distribution in the xerogels is strongly influenced by the gel-processing temperature. At temperatures near 150°C ligation with lactate groups can be nearly suppressed, resulting in maximum Al/P connectivity in the gel. Annealing the gels at temperatures near 400°C produces significant structural rearrangements, resulting in a glassy network that has close structural similarity to the glasses derived from the usual melt-cooling procedure at 1100–1450°C. This has been confirmed by extensive ²⁷Al, ³¹P and ²³Na MAS NMR as well as ²⁷Al{³¹P} and ²⁷Al {¹H} double resonance experiments. Compared to melt-cooling, the sol–gel process permits a significant extension of the glass-forming region towards higher alumina contents.     

Dielectric matrices with air cavities as a waveguide photonic crystal

Frequency dependences of the transmission coefficient of a microwave photonic crystal that represents a structure containing alternating layers of ceramic material (Al₂O₃) with a relatively large number of cavities and foam plastic are studied in the presence and absence of distortions of the periodicity of a photonic structure. The frequency dependences of the transmission coefficient can be analyzed using a model of effective medium that makes it possible to consider the interaction of electromagnetic wave and photonic crystal using a transfer matrix of a 1D photonic crystal. The band character of the frequency dependence of the transmission coefficient of the photonic crystal related to the periodicity of the photonic crystal in the transverse plane for the waveguide with a standard cross section is not manifested in a certain range of material permittivities.     

Dielectric properties of liquid crystals in polycapillary matrices

This paper reports on the results of investigations into the dielectric properties of liquid crystals embedded in polycapillary matrices and describes a technique for their measurement. It has been revealed that the chemical structure of the rigid core and the length of mobile alkyl groups of liquid-crystal molecules of the alkylcyanobiphenyl group substantially affect the equilibrium configuration of the liquid-crystal director in capillaries. The reorientation of liquid-crystal molecules embedded in capillaries in the nematic phase under the influence of an external magnetic field has been investigated.     

Small-angle X-ray scattering study of the structure of glassy nanoporous matrices

The structure of high-silica glassy nanoporous matrices prepared from two-phase glasses has been investigated using the small-angle X-ray scattering technique. Parameters of materials, such as the density, porosity, specific surface area, average nanopore radius, average radius of scattering particles filling the pore space, and their fractal dimensions, have been determined. The dependence of the obtained structural parameters on the conditions of chemical treatment of glasses has been established. It has been demonstrated that the results obtained are in good agreement with porosimetry and electron microscopy data.     

Dielectric behavior of sodium borate glasses

The dielectric constant and the electrical conductivity of the transparent glasses in the composition 3Na₂O-7B₂O₃ (NBO) were investigated in the 100 Hz–10 MHz frequency range at various temperatures. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 0.76 ± 0.02 eV, close to that (0.74 ± 0.02 eV) obtained from DC conductivity studies. The frequency-dependent electrical conductivity was analyzed using Jonscher’s power law. Temperature-dependent behavior of the frequency exponent (n) suggested that the correlated-barrier hopping model was the most appropriate to rationalize the electrical transport phenomenon in NBO glasses.