Interfacial polarization in piezoelectric fibre–polymer composites

Polymer composites of an epoxy resin matrix filled with PZT fibres were studied by means of dielectric spectroscopy in the frequency range 0.1 Hz to 100 kHz and temperature interval from 80 °C to 170 °C. An interfacial or a Maxwell–Wagner–Sillars relaxation process was revealed in the frequency range between 0.1 Hz and 10 Hz and temperatures above the glass transition. This interfacial relaxation was found to follow the Debye law for the distribution of relaxation times.     

Slow and fast dynamics in glycerol–water mixtures

We discuss the relaxation dynamics of glycerol–water mixtures as studied by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). BDS studies were performed in a frequency range of 1 Hz to 250 MHz at temperatures ranging from 173 to 323 K and DSC measurements were made between 138 and 313 K. The experimental results obtained for the glycerol-rich mixtures in terms of dielectric loss ‘master plots’ suggest that the main dielectric relaxation process, as well as the high frequency ‘excess wing’ and dc-conductivity, follow the same temperature dependence. This result indicates that all of these processes are based on the same physical origin. A new phenomenological relationship for the complex dielectric permittivity is proposed. The structural and dynamic properties of glycerol–water mixtures are discussed. The experimental data for water-rich mixtures show the existence of a critical concentration of 40 mol% of glycerol that relates to the numbers of hydrogen bonds of glycerol and of water molecules. Below this concentration, water cooperative domains appear, coexisting with the glycerol cooperative domains. Below 20 mol% of glycerol, ice nanocrystals appeared that led to three relaxation processes; result from ice, mesoscopic glycerol–water domains, and water on the interface between former two.     

Relaxation in mixed alkali fluoride glasses

We have investigated the dynamics of alkali cations as well as fluorine anions in non-oxide fluoride glasses with a total alkali fluoride content varying from 16 to 35 mol% in the frequency range from 10 Hz to 2 MHz and in the temperature range from room temperature to just below the glass transition temperature. We have shown that the dc and ac conductivity, crossover frequency and conductivity relaxation frequency exhibit a minimum in mixed alkali fluoride glasses, where anions also participate in the diffusion processes in addition to cations, unlike mixed alkali oxide glasses and crystals. We have observed lower dimensionality of the conduction pathways in mixed alkali fluoride glasses compared to that in the single alkali glasses. We have shown that the relaxation dynamics in mixed alkali fluoride glasses is independent of temperature.     

Molecular dynamics in glass-forming poly(phenyl methyl siloxane) as investigated by broadband thermal,dielectric and neutron spectroscopy

The molecular dynamics of glass-forming poly(methyl phenyl siloxane) (PMPS) is studied by thermal (10⁻³–5 × 10² Hz), dielectric (10⁻³–10⁹ Hz) and neutron (5 × 10⁸–10¹² Hz) spectroscopy. Because of the broad frequency range of 15 orders of magnitude the study provides a precise determination of glassy dynamics in a wide temperature range using different probes. The relaxation rates extracted from the different methods agree quantitatively in both their absolute values and in their temperature dependencies. A detailed analysis of the temperature dependence of the relaxation rate f_p by a derivative technique shows that the α-relaxation of PMPS has to be characterized by a high and a low temperature branch separated by a crossover temperature T_B = 250 K. In both temperature ranges the temperature dependence of f_p has to be described by Vogel/Fulcher/Tammann laws with different Vogel temperatures. Also the analysis of the dielectric strength in its temperature dependence gives a crossover behavior from a low to a high temperature region with a similar value of T_B. T_B can be interpreted as onset of cooperative fluctuations and the formation of dynamical heterogeneities. The dependence of the relaxation rate on the scattering vector Q extracted from neutron scattering obeys a power law τ ∼ Q^−Slope, where the power Slope varies between Slope = 2 and Slope = 3.5 with increasing temperature. This anomalous dependence of the relaxation time on the momentum transfer is discussed in terms of dynamic heterogeneities in the underlying motional processes even at temperatures above T_B. Besides the segmental dynamics the fast Methyl group rotation is considered as well. The relaxation rates of this process have an activated temperature dependence with an activation energy of 8.3 kJ/mol. The data were discussed in the framework of the threefold jump model were the incoherent elastic scattering from ‘fixed’ atoms which are frozen on the time scale of the Methyl group rotation was taken into account.     

Nearly constant dielectric loss of polyhydric alcohols

Complex permittivity measurements have been performed on a series of polyhydric alcohols (glycerol, threitol, xylitol and sorbitol) and mixtures of glycerol–xylitol and xylitol–sorbitol in the frequency range between 100 Hz and 1 MHz at temperatures from 293 K down to 50 K. It was found that all the systems including the mixtures show the nearly constant dielectric loss (NCL) at temperatures far below the glass transition temperature. The parameters describing the NCL depend on the number of carbons in the molecules. This relation can also be applied for the mixture with the mean values for the number of carbons. The parameters describing the behavior of the α process, such as the fragility index, depend the number of carbons in this series of polyhydric alcohols. Degree of freedom in the intermolecular interactions connected with the fragility index can be considered to relate to the NCL. This is consistent with the caged dynamics as a possible microscopic origin for the NCL. Although the fast β process is not denied by the NCL, coexistence of these processes being able to explain the dielectric loss minima, should be examined experimentally in future.     

Dielectric monitoring of curing process for some epoxide-amine thermosets

Three recently synthesized epoxy monomers were studied. All the monomers form a nematic phase in temperatures above 80 °C. This paper presents the dielectric response of pure monomers in the frequency range of 10⁶–10⁹ Hz as well as its changes occurring in the course of crosslinking with 4,4′-diaminodiphenylmethane used as curing agent. A relaxation process related to molecular motions is clearly visible in this frequency range for each of the monomers, though its characteristics are somewhat different in particular cases. The evolution of the relaxation process is visible in the course of curing. The dynamics of curing observed through dielectric data is compared with the results of differential scanning calorimetry measurements.     

Vitrification,relaxation and free volume in glycerol–water binary liquid mixture: Spin probe ESR studies

Glass transition and relaxation of the glycerol–water (G–W) binary mixture system have been studied over the glycerol concentration range of 5–85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition, sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol% is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.     

The study of removing hydroxyl from silica glass

The removal of hydroxyl from silica glass produced by melting quartz powder under an atmosphere containing hydrogen was investigated. After heat-treatment at the temperature range (700–1200 °C) in nitrogen atmosphere, the effective hydrogen diffusion coefficients were evaluated based on the law of nonsteady-state diffusion. The activation energy obtained is 254 kJ mol⁻¹ for the dehydroxylation process in the heat-treatment temperature range of 700–900 °C, and a different activation energy calculated is 32 kJ mol⁻¹ in the temperature range of 900–1200 °C. The activation energies for the dehydroxylation process at the temperature (700–900 °C) and the higher temperature (900–1200 °C) correspond to the binding energy of SiO–H bond and the activation energy for the diffusion of hydrogen in silica glass respectively, which indicate there is a change of mechanism for dehydroxylation with heat-treatment temperature.     

Low temperature dielectric dispersion and electrical conductivity studies on Fe2O3 mixed lithium yttrium silicate glasses

Lithium yttrium silicate glasses mixed with different concentrations of Fe₂O₃ of the composition (40 ? x) Li₂O–10Y₂O₃–50SiO₂: x Fe₂O₃, with x = 0.3, 0.5, 0.8, 1.0, 1.2 and 1.5 (all in mol%) were synthesized. Electrical and dielectric properties including dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, impedance spectra as well as electric moduli, M(ω), over a wide continuous frequency range of 40 Hz to 10⁶ Hz and in the low temperature range 100 to 360 K were measured as a function of the concentration of Fe₂O₃. The dc conductivity is also evaluated in the temperature range 100 … 360 K. The temperature and frequency dispersions of dielectric constant as well as dielectric loss have been analyzed using space charge polarization model. The ac and dc conductivities have exhibited increasing trend with increasing Fe₂O₃ content beyond 0.5 mol%, whereas the activation energy for the conductivity demonstrated decreasing tendency in this dopant concentration range. Both quantum mechanical tunneling (QMT) and correlated barrier hopping models (CBH) were used for clarification of ac conductivity origin and the corresponding analysis has indicated that CBH model is more appropriate for this glass system. For the better understanding of relaxation dynamics of the electrical properties we have drawn the scaling plots for ac conductivity and also electric moduli. The plots indicated that the relaxation dynamics is independent on temperature but depends on concentration of Fe₂O₃. The dc conductivity is analyzed using small polaron hoping model. The increase of conductivity with the concentration of Fe₂O₃ beyond 0.5 mol% is explained in terms of variations in the redox ratio of iron ions in the glass network. The results were further analyzed quantitatively with the support of experimental data from IR, optical absorption and ESR spectral studies. The overall analysis has indicated that Li₂O–Y₂O₃–SiO₂ glasses containing more than 0.5 mol% of Fe₂O₃ are more suitable for achieving good electrical conductivity in these glasses.     

Isobaric and isochoric properties of decahydroisoquinoline,an extremely fragile glass-former

Pressure–volume–temperature (PVT) measurements were obtained on decahydroisoquinoline (DHIQ). From the resulting equation of state in combination with previously reported dielectric relaxation data, an analysis of the volume contribution to the dynamics was carried out for this very fragile glass-former (isobaric fragility, m_P = 163). We find that the ratio of the isochoric and isobaric fragilities equals 0.71 ± 0.02, reflecting a strong temperature effect, consistent with the large fragility. The relaxation times superpose when plotted versus temperature times the specific volume raised to the 3.55 power. This is a larger value of the exponent than expected based on the fragility of DHIQ. The implication is that for molecular glass-formers, the classical Lennard-Jones 6–12 repulsive potential may represent the limit for fragile liquids.     

Electrical properties of A2.6+xTi1.4−xCd(PO4)3.4−x (A = Li,K; x = 0.0–1.0) phosphate glasses

Electrical properties of A_2.6+xTi_1.4−xCd(PO₄)_3.4−x (A = Li, K; x = 0.0–1.0) phosphate glasses are investigated over a frequency range from 42 Hz to 1 MHz at different temperatures. Impedance spectroscopy is used to separate the bulk conductivity from electrode effect of electrical conductivity data. The bulk dc conductivity is Arrhenius activated, with activation energies and pre-exponential factors following the Meyer–Neldel rule. The real part of ac conductivity shows universal power law feature. The variation of dielectric constant with frequency is attributed to ion diffusion and polarization occurring in the phosphate glasses. The frequency dependent imaginary part of electric modulus M″(ω) plot shows non-Debye feature in conductivity relaxation. The Kohlrausch–Williams–Watts stretched exponential function was used to describe the modulus spectra and the stretching exponent β is found to be temperature independent. Scaling in M″(ω) shows that the electrical relaxation mechanisms are independent of temperature for given composition at different temperatures.     

Real time dielectric monitoring of glass transition in n-vinyl pyrrolidone polymerization

Real time dielectric spectroscopy was used for monitoring the dynamics during liquid glass transition in radical bulk polymerization of n-vinyl pyrrolidone. Two different relaxation mechanisms were identified. Initially segmental α-relaxation was dominant. Subsequently, contribution from slower motions became more significant and ε′(t_r, ω) underwent maxima in all frequency bands up to 10 MHz. Peak amplitude increased and the occurring time was delayed with decreasing frequency. The slow region dynamics were similar to the dynamics of Chamberlin’s domain-like model of glass transition. The glassy phase is formed by a segmental relaxation and a relaxation due to glassy regions. The characteristic relaxation times of slow and segmental motions were well described by a modified Vogel–Fulcher–Tammann relation. The high frequency behavior, associated with the segmental motions, is well described by Havriliak–Negami and Kohlrausch–Williams–Watts formulas, which did not provide satisfactory fittings for the dynamics of slow regions. Both real and imaginary parts of the dielectric data were fully described by a complex dielectric relaxation function, the parameters of which are found by the eigen-coordinates (EC) method.     

Terahertz spectroscopy of polar solute molecules in non-polar solvents

Low frequency spectra of liquid solutions of non-polar solvents were measured in the frequency range of 15–80 cm⁻¹ at room temperature by terahertz time-domain spectroscopy to investigate the solute–solvent interaction. The extinction coefficient of the solutions with polar solutes decreases as a function of frequency, whereas that of a non-polar solute increases. It is concluded that the observed spectral change of the polar solute is caused by fast reorientational dynamics due to librational motion of solutes.     

Semi-interpenetrating polymer networks based on polyurethane and poly(2-hydroxyethyl methacrylate): Dielectric study of relaxation behavior

The study of molecular dynamics by broadband dielectric spectroscopy (BDS) is presented for polyurethane (PU), poly(2-hydroxyethyl methacrylate) (PHEMA) and for semi-IPNs based on PU and PHEMA synthesized by photopolymerization. The dielectric properties were performed in wide range of frequencies and temperatures with the goal to establish the relation between the relaxations and the structure. Five relaxation phenomena were finally detected for PHEMA : γ-, βsw-, β-relaxations at low temperatures and α-relaxation at 150 °C at high frequencies plus ionic conductivity relaxation which starts at 0 °C. For semi-IPNs the overlapping of γ- and βsw-relaxations of PHEMA (?125/?75 °C), then with increasing the temperature α-relaxation in PU (?75/0 °C), next ionic conductivity relaxation which starts at 0 °C, and finally the α-relaxation of PHEMA (+125/+170 °C) were detected. The α-relaxation of PHEMA in semi-IPNs shifts to lower temperatures and became broader with increasing amount of PU due to incomplete phase separation in the system and formation of interphases. The dielectric relaxation phenomena were fitted with Havriliak–Negami equation. Activation energy, τ_o and α parameters were calculated. For α-relaxations corresponding dielectric characteristics have been determined from Vogel–Fulcher–Tammann equation. The relaxation map for investigated PU, PHEMA and semi-IPNs was built.     

Relaxation of polaronic charge carriers in lithium manganese spinels

Lithium manganese spinels Li_1+xMn_2−xO₄, 0 ⩽ x ⩽ 0.33, were prepared by wet chemistry technique followed by heat-treatment at 750 °C or 800 °C. Differential scanning calorimetry was used to reveal phase transitions. Electrical properties were studied by impedance spectroscopy. LiMn₂O₄ exhibited phase transition below room temperature. The transition, seen as an exothermic event in DSC and a steep decrease of conductivity upon cooling, was sharp in sample sintered at 800 °C and broadened over a range of temperature in sample sintered at 750 °C. In the low temperature phase of LiMn₂O₄, two relaxations of similar strength were observed in the frequency dependent permittivity. The low frequency process was identified as relaxation of charge carriers since the relaxation frequency followed the same temperature dependence as the dc conductivity. The high frequency process exhibited milder temperature dependence and was attributed to dipolar relaxation in the charge-ordered structure. The dipolar relaxation was barely visible in Li substituted samples, x ⩾ 0.05, which did not undergo structural phases transition. Measurements extended to liquid nitrogen temperature showed gradual lowering of the activation energy of conductivity and relaxation frequencies, behavior typical for phonon-assisted hopping of small polarons.     

Emission and local structure of rare-earth ions in chalcogenide glasses

Local structures of rare-earth ions in Ge–Ga–S–CsBr glasses were investigated to understand the structural origin on the emission property enhancement. The frequency of the phonon vibration controlling the multiphonon relaxation was changed to 245 cm⁻¹ due to the formation of Ga–Br bonds with CsBr addition to sulfide glasses. Formation of this new chemical bond was also confirmed from the phonon side band spectra of Eu³⁺ ions. Analyses of the EXASF spectra proved that Tm³⁺ ions were surrounded by approximately seven S ions in Ge_0.25Ga_0.10S_0.65 glass but were coordinated by ∼6 Br ions in the glass with 10 mol% of CsBr.     

Electrical conductivity and dielectric relaxation in non-crystalline films of tungsten trioxide

Amorphous tungsten trioxide (a-WO₃) thin films were prepared by thermal evaporation technique. The electrical conductivity and dielectric properties of the prepared films have been investigated in the frequency range from 100 Hz to 100 kHz and in the temperature range 293–393 K. In spite of the absence of the dielectric loss peaks, application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation. The frequency dependence of σ(ω) follows the Jonscher’s universal dynamic law with the relation σ(ω) = σ_dc + Aω^s, where s is the frequency exponent. The conductivity in the direct regime, σ_dc, is described by the small polaron model. The electrical conductivity and dielectric properties show that Hunt’s model is well adapted to a-WO₃ films.     

Luminescence and absorption spectroscopy of Sn-related impurity centers in silica

We report an experimental study on the absorption and luminescence spectra of oxygen deficient point defects in Sn-doped silica. The absorption band at 4.9 eV (B_2β band) and the two related photoluminescence bands at ∼4.2 eV (singlet–singlet emission, S₁ → S₀) and at ∼3.2 eV (triplet–singlet emission, T₁ → S₀), linked by a thermally activated T₁ → S₁ inter-system crossing process (ISC), are studied as a function of temperature from 300 to 20 K. This approach allows us to investigate the dynamics properties of the matrix in the surroundings of the point defects and the effects of local disorder on the two relaxation processes from S₁: the radiative channel to S₀ and the ISC process to T₁. We observe that the S₁ → S₀ decay kinetics at higher temperatures do not follow a single-exponential law and the ISC rate shows a temperature dependence that cannot be rationalized by a single activation process, suggesting the presence of a complex landscape of configurational energies. The comparison with analogous data for Ge-doped silica reveals that the local dynamics of the matrix, the defect–matrix electron–phonon coupling, and the ISC rate dispersion are not substantially modified by the isoelectronic and isostructural substitution Sn–Ge. On the contrary, the Sn-related ISC process is ∼5 times more efficient than the Ge-related one. Since we observed that the coupling with local phonons increases the ISC efficiency by four order of magnitudes in the investigated temperature range, the reported data strongly suggest that, even if the presence of the spin–orbit coupling is needed for ISC processes, it has not play a primary role in the ISC processes in silica, where it acts as a homogenous and temperature-independent scale factor.     

Dielectric behavior and impedance spectroscopy of bismuth iron phosphate glasses

The electrical and dielectrical properties of Bi₂O₃–Fe₂O₃–P₂O₅ glasses were measured by impedance spectroscopy in the frequency range from 0.01 Hz to 4 MHz and over the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. With increasing Fe(II) ion content from 17% to 34% in the bismuth-free 39.4Fe₂O₃–59.6P₂O₅ and 9.8Bi₂O₃–31.7Fe₂O₃–58.5P₂O₅ glasses, the dc conductivity increases. On the other hand, the decrease in dc conductivity for the glasses with 18.9 mol% Bi₂O₃ is attributed to the decrease in Fe₂O₃ content from 31.7 to 23.5 mol%, which indicates that the conductivity for these glasses depends on Fe₂O₃ content. The conductivity for these glasses is independent of the Bi₂O₃ content and arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electronic conduction. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency the dispersion was investigated in terms of dielectric loss. The thermal activated relaxation mechanism dominates the observed relaxation behavior. The relationship between relaxation parameters and electrical conductivity indicates the electronic conductivity controlled by polaron hopping between iron ions. The Raman spectra show that the addition of up to 18.9 mol% of Bi₂O₃ does not produce any changes in the glass structure which consists predominantly of pyrophosphate units.     

Structural studies of lead aluminate glasses

Lead aluminate melts were quenched rapidly with a roller quencher and bulk glasses were formed over a composition range from 72.5 to 80.0 mol% PbO. Pulsed neutron diffraction, ²⁷Al MAS NMR and Raman spectroscopy were used to study the structure of a series of these glasses. The results show that in the glasses the aluminium is four coordinated by oxygen across the compositional range, with a bond length of about 1.76 Å. The Pb–O peak in the neutron correlation function is asymmetric, and it can be modelled in terms of two bond lengths of ∼2.25 Å and ∼2.47 Å, with the majority of the coordination at the shorter distance. There is evidence that most or all of the lead ions are on asymmetric sites, coordinated by three oxygens in a trigonal pyramid arrangement. Both the neutron diffraction and Raman results indicate that the Pb–O bond lengths become shorter with increasing lead content.