Effect of growth defects on microwave properties in epitaxial Ba0.5Sr0.5TiO3 thin films grown on (001) MgO by pulsed laser deposition

Ba_0.5Sr_0.5TiO₃ (BSTO) films have been grown heteroepitaxially on (001) MgO substrates by pulsed laser deposition (PLD) to fabricate microwave phase shifters for the wide frequency range 45 MHz–50 GHz. Both as-grown and ex situ annealed films have a cube on cube epitaxial relationship with ?100?BSTO//?100?MgO. Threading dislocations are the dominant defects, mostly with Burgers vectors b = ?101?. Growth at 10^?1 mbar oxygen pressure, compared to 10^?4 mbar, resulted in significantly better properties. Ex situ annealing of the film grown at 0.1 mbar resulted in a reduction of 40% in threading dislocation density and a 40% increase in dielectric tunability.     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.     

Thermal equation of state of goethite (α-FeOOH)

ABSTRACT

The pressure–volume–temperature (P–V–T) equation of state (EoS) of natural goethite (α-FeOOH) has been determined by an X-ray diffraction study using synchrotron radiation. Fitting the volume data to the third-order Birch–Murnaghan EoS yielded an isothermal bulk modulus, B₀ of 85.9(15)?GPa, and a pressure derivative of the bulk modulus, B′, of 12.6(8). The temperature derivative of the bulk modulus, (?B/?T)_P, was –0.022(9)?GPa?K^?1. The thermal expansion coefficient α₀ was determined to be 4.0(5)?×?10^?5?K^?1.     

Dielectric and structural relaxation phenomena in Na0.5Bi0.5TiO3 single crystal

Abstract

Dielectric permittivity studies of Na_0.5Bi_0.5TiO₃ single crystals in a broad range of frequency up to 10 MHz and temperature 300—823 K are reported. In this temperature range dielectric dispersion below 1 MHz has been found. The obtained data were fitted to the Cole-Cole relation. The mean relaxation time τ is strongly temperature dependent (0.04 ? 2.6 × 10^?5 s). A remarkable hysteresis effect in the values of τ on cooling and heating took place. The Δε(T) dependence (the maximal value of Δε ～ 400) is similar to the global ε′(T) response at low frequency. An isothermal structural transformation in Na_0.5Bi_0.5TiO₃ was observed by X-ray measurements. The order of the time in which the transformation takes place (～300 minutes) corresponds to the time in which the strongest time evolution of electric permittivity and time changes of dielectric dispersion were detected.     

Flow Injection Kinetic Spectrophotometric Determination of Cerium Based on the Decolorization Reaction Between Arsenazo III and Cerium (IV)

ABSTRACT

Trace amounts of cerium were analyzed by flow injection kinetic spectrophotometry, based on the decolorization reaction between arsenazo III and Ce(IV) in sulfuric acid medium at room temperature. The absorbance difference (ΔA) of decolorization was linear with the concentration of Ce(IV). The flow injection technique was used to precisely control the timing. Under the optimum conditions, the determination of Ce(IV) in the range 0.0–8.0 µg mL^?1 with a correlation coefficient (r) of 0.9982, the regression equation was ΔA = 0.0014 + 0.0406c (µg mL^?1). The detection limit (3σ) of 0.2 µg mL^?1 was achieved at a sampling frequency of 60 h^?1. The proposed method was applied to the analyses of Ce in soil successfully.     

Elastic,impedance spectroscopic and dielectric properties of TiO2 doped nanocrystalline NiCuZn spinel ferrites

ABSTRACT

Nanocrystalline Ni_0.4Cu_0.3Zn_0.3Fe₂O₄ ferrites doped with TiO₂ (0–10?wt %) were prepared by the sol-gel method. Elastic properties of synthesized samples were studied with the help of ultrasonic pulse transmission method. The elastic constants initially increase with an increase in TiO₂ up to 1?wt % and then decline. LCR-Q meter was used to study the dielectric properties within 50?Hz to 5?MHz range of the frequency. The dielectric constant (?′) and dielectric loss tangents were decreased continuously with increased frequency for all the selected samples at room temperature revealing normal dielectric behavior of ferrites. Also, the AC conductivity was increased with an increase in the frequency for all the selected samples. Cole-Cole plots were obtained for all investigated samples and showed single semicircle which indicates that the electrical conduction process appears only due to grain boundaries.     

Effect of ion beam irradiation on palladium (II) acetyl acetonate dispersed in polymer matrix

Composites, containing different concentrations of palladium (II) acetylacetonate in polymethyl methacrylate (PMMA) matrix were prepared by vigorous mixing. PMMA was prepared by solution polymerization technique. The composites were irradiated with a 120 MeV Ni¹⁰⁺ beam at two different fluences of 1×10¹¹ and 5×10¹² ions/cm² to study ion-induced effects on their dielectric, structural properties and surface morphology. AC electrical properties of these samples were studied in the frequency range 100 Hz to 10 MHz. The dielectric permittivity/loss shows frequency dependent behavior and it obeys the universal law of dielectric (i.e. ?α f ^n?1) for pristine and irradiated samples at high frequency. The crystalline size and crystallinity of the composites were studied by X-ray diffraction analysis. Decrease in peak intensity after irradiation signifies the amorphization which is also responsible for decrease in T _g as obtained by means of differential scanning calorimetry measurement. Fourier transform infrared spectra also support this result. Surface roughness increases upon irradiation as observed from scanning electron microscopy.     

Dispersion of dielectric constants in bismuth strontium ferrite (Bi,Sr)FeO<Subscript>3 − <Emphasis Type="Italic">x</Emphasis></Subscript>—Variable-valence perovskite-structure solid solution

The reflection spectrum R(ν) and transmission spectrum Tr(ν) of polycrystalline solid solutions Bi_0.5Sr_0.5FeO_2.75 are studied for the first time using submillimeter and IR spectroscopy in the frequency range 7 < ν < 4000 cm^?1 at temperatures of 10–300 K. A large difference is found between the magnitudes of the dielectric susceptibility measured by contact (at a frequency of 10³ Hz) and noncontact (THz range) methods. It is suggested that powerful relaxation excitations exist at frequencies below 100 cm^?1 (“subphonon” region). The possible origin of the excitations is discussed.     

Dielectric behavior of TiC–PVDF nanocomposites

TiC/PVDF nanocomposite is prepared via simple blending and hot pressing route. Percolation theory was employed to explain the dielectric behavior of the TiC/PVDF composites. The dependence of the dielectric properties of the composite on both volume fraction of the filler and frequency is investigated. High dielectric constant (? = 540) and low loss (tan δ = 0.48) of the composites at 100 Hz have been observed near the percolation threshold (0.12). The composites show a weak frequency dependence towards the high frequency range (10–100 kHz), regardless of the TiC content. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.     

In situ study of self-ion irradiation damage in W and W–5Re at 500 °C

In situ self-ion irradiations (150?keV?W⁺) have been carried out on W and W–5Re at 500?°C, with doses ranging from 10¹⁶ to 10¹⁸ W⁺m^?2 (～1.0?dpa). Early damage formation (10¹⁶W⁺m^?2) was observed in both materials. Black–white contrast experiments and image simulations using the TEMACI software suggested that vacancy loops were formed within individual cascades, and thus, the loop nucleation mechanism is likely to be ‘cascade collapse’. Dynamic observations showed the nucleation and growth of interstitial loops at higher doses, and that elastic loop interactions may involve changes in loop Burgers vector. Elastic interactions may also promote loop reactions such as absorption or coalescence or loop string formation. Loops in both W and W–5Re remained stable after annealing at 500?°C. One-dimensional hopping of loops (b?=?1/2 ?111>) was only seen in W. At the final dose (10¹⁸W⁺m^?2), a slightly denser damage microstructure was seen in W–5Re. Both materials had about 3–4?×?10¹⁵ loops m^?2. Detailed post-irradiation analyses were carried out for loops of size???4?nm. Both b?=?1/2 ?111? (～75%) and b?= ?100> (～25%) loops were present. Inside–outside contrast experiments were performed under safe orientations to determine the nature of loops. The interstitial-to-vacancy loop ratio turned out close to unity for 1/2 ?111? loops in W, and for both 1/2 ?111? and ?100? loops in W–5Re. However, interstitial loops were dominant for ?100? loops in W. Re seemed to restrict loop mobility, leading to a smaller average loop size and a higher number density in the W-Re alloy.     

Specific features of the dielectric spectrum of CaCu3Ti4O12 in the low-frequency range

The dielectric spectra of CaCu₃Ti₄O₁₂ ceramics with giant values of the dielectric constant have been presented. The spectrum exhibits Debye dispersion with an activation energy of 0.075 eV in the high-frequency range of 10⁶–10⁷ Hz, and a characteristic plateau has been seen in the frequency dependence of the dielectric constant in the range of 10⁴–10⁵ Hz. A considerable increase in the loss factor ?″ has been observed in the low-frequency part of the spectrum and a capacitive-to-inductive impedance transition has been revealed in some samples at a frequency below 10^?2 Hz. The causes of this transition have been discussed.     

Studies on the Dielectric Behavior of Silica-Filled Butyl Rubber Vulcanizates After Cyclic Deformation

Abstract

The broadband dielectric spectroscopy (10^?3–10⁶ Hz) is used to study the effect of stress-strain cycles on the dielectric properties of butyl rubber vulcanizates filled with silica. The influence of chemical modification of the surface of the silica by silane coupling agent (Si69) also was investigated. In addition Transmission Electron Microscopy (TEM) and Differential Scanning Calorimetry (DSC) were carried out. Dielectric investigations of the samples were done after stress-strain cycles with maximum elongation 26%, 40%, 60%, and 80% from elongation at break, respectively. It was found that the dielectric properties recovered after storage at room temperature for about one year.     

Dielectric relaxation in ferroelectric (CH3)2NH2AL(so4)2 · 6H2O crystal

Abstract

This paper presents the results of the investigation of dielectric dispersion and ultrasonic velocity in the ferroelectric (CH₃)₂NH₂Al(SO₄)₂ · 6H₂O crystal. The crystal shows a critical slowing down process of polarization with an extremely long relaxation time of the dipole system (τ = 1.6 · 10^?7s at the phase transition point). The dielectric response over the frequency range up to 56 GHz in the paraelectric phase can be well described in terms of a monodispersive Debye-type formula. The activation energy of dipoles in the paraelectric phase is 0.11 eV = 8.5 kT_c . The results show that the proper ferroelectric phase transition is nearly critical and of the order-disorder type.     

Possible mechanisms of dielectric relaxation of liquid water and calculation of the temperature dependence of the complex permittivity of water

The spectra of the complex dielectric permittivity and absorption of water (H₂O) in the frequency range 0–1000 cm^?1 are calculated for a wide temperature interval. Using the method of autocorrelation functions, the dielectric response of dipoles rotating in potential wells of three types is found. The majority of dipoles (about 90%) rotate in a deep and comparatively narrow potential well, whose profile resembles an upside-down hat. Such a potential models a molecular structure with strongly bent and/or broken hydrogen bonds. The hat model describes the complex permittivity in the low-frequency (Debye) range and in the range 300–1000 cm^?1. The remaining dipoles (～10%) execute harmonic vibrations of two types: rotational vibrations about the equilibrium direction of a hydrogen bond and translational vibrations along this direction. These types of motion yield the dielectric response in the frequency range 10–300 cm^?1. This response is described by the Lorentz lines in terms of the harmonic oscillator model and the truncated parabola model. The hat–harmonic oscillator–truncated parabola composite model provides good agreement with experimental spectra. The lifetimes of the three types of motion considered are about 10, 0.2, and 0.05 ps, respectively. They characterize (i) tetrahedral translations of molecules accompanied by their rotations, (ii) librations of dipoles in the hatlike potential well, and (iii) elastic interactions of hydrogen-bonded molecules. Based on data of independent methods of investigation, it is concluded that the temperature 300 K is a singular point with respect to the properties of liquid water.     

Ac electrical conductivity and dielectric relaxation behavior of amorphous Selinum36 Antimony31Cubber33 thin films

ABSTRACT

The alternating-current (Ac) conductivity measurements and dielectric behaviors were observed in the range of temperature (from 303 to 393?K) and in the frequency range from 10² to10⁶?Hz for amorphous films of Selinum₃₆ Antimony₃₁ Cubber₃₃ chalcogenide glass. The ac conductivity has temperature dependency and the frequency dependency. The reduction of the exponent S values with raising temperature was introduced with the correlated barrier hopping model. The maximum height of the barrier W_M for Sellinum₃₆ Antimony₃₁Cubber₃₃ films is reliable with carrier hopping over a potential barrier. The number of localized states per unit volume at the Fermi level enhances with the elevation of ambient temperature of the film sample. Both dielectric constant ε₁ and loss ε₂ increase with the rise of temperature rising and decrease with frequency. The computation of the dielectric modulus M^/ and M^// revealed that the interfacial is the most suitable polarization type.     

Super-linear frequency dependence of ac conductivity of disordered Ag2S–Sb2S3 at cryogenic temperatures

The ac conductivity of a new class of disordered solids, i.e. mechanochemically synthesized amorphous fast ion conducting Ag₂S–Sb₂S₃ materials, has been investigated in the audio frequency range (10–10⁷?Hz) down to cryogenic temperatures (～10?K). The conductivity spectra exhibit the usual signature of a disordered system at higher temperatures, well described by the Jonscher power law (JPL) i.e., σ′(ω)?=?σ _dc?+?A(T)ω*, although the frequency exponent (n?<?1) is found to be a weak function of temperature. However, as the temperature is lowered, the frequency width of the σ _dc region decreases gradually and that of the JPL region increases. Eventually, the σ _dc region disappears and the JPL region alone dominates the spectrum. However, at the lowest temperatures, both the σ _dc and JPL regions disappear and σ′(ω) obeys a super-linear power law (SPL) (σ′?∝?ω^m , m?≥?1). It is observed that the SPL has strikingly similar characteristics to the well-established nearly-constant-loss (NCL) behaviour corresponding to m?=?1. Both SPL and NCL appear in the same time–temperature (low-temperature/low-frequency) domain. Furthermore, in both cases the conductivity is a distinctly weak function of temperature but quite sensitive to frequency, and the SPL/NCL?→?JPL crossover frequency is thermally activated with almost the same energy as the ac activation energy. The presence of the SPL is further manifested in the form of a well-defined minimum in the dielectric loss, ε″(ω), spectra. It is therefore proposed that the entire low-temperature/low-frequency spectra can be described by a modified Jonscher power law, σ′(ω)?=?σ _dc(T)?+?A(T) ωⁿ ?+?B(T)ω^m , m?=?1 (NCL), m?>?1 (SPL), where the second term with n?<?1 accounts for the JPL and the third term with m?≥?1 accounts for SPL/NCL. The results and some other low-temperature/low-frequency conductivity data are consistent with an asymmetric double well potential (ADWP) model.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

The influence of strain rate on the visibility of dislocations in transmission electron microscopy images of deformed Ti–6 wt% Al–4 wt% V and in Timet 550

Samples of Ti–6?wt%?Al–4?wt%?V and Timet 550 (Ti–4?wt%?Al–4?wt%?Mo–2?wt%?Sn–0.5?wt%?Si) have been subjected to strain rates between 10^?1 and 10³?s^?1and detailed examination of the dislocation structure in the α grains has been carried out using transmission electron microscopy (TEM). For samples deformed to a strain of 0.1 at 10^?1?s^?1, detailed analysis of the defects can be carried out using all diffracting vectors and the presence of (c +?a) dislocations and a dislocations thus confirmed. In contrast, for samples strained to the same strain of 0.1 but at 5?s^?1, it is not possible to obtain images of dislocations when using any diffracting vectors other than 0002. Thus the presence of dislocations which have a Burgers vector containing a c component can be confirmed in the samples strained at 5?s^?1 but the presence of a-component dislocations can only be inferred from TEM of these samples because of the difficulty of obtaining images with diffracting vectors other than 0002. Limited observations on samples strained at 10³?s^?1 show that similar difficulties are found in imaging dislocations as are found in samples deformed at 5?s^?1 but at this strain rate, the highest used, the difficulties are reduced since images can be obtained in some grains using diffracting vectors other than 0002. These results are discussed in terms of the nature of damage as a function of strain rate and the factors that influence contrast from dislocations in crystals.     

A Ketene Intermediate in 3-Cyclopentenone Photolysis : Matrix-Isolation and Gas Phase Experiments

Abstract

Photolysis experiments are performed at λ  230 nm on argon matrix-isolated and on gas phase 3-cyclopentenone ( 1 ); in both cases, a ketene intermediate (KE) is detected (FT-IR spectra : 2121–2126 cm^?1 in argon matrix; 2066–2210 cm^?1 in gas phase). 1,3-butadiene ( 2 ) and carbon monoxide are the reaction products. Two first-order consecutive photochemical processes occur 1 ^k1 > KE ^k2 > 2 + CO with k₁ = 1.7 10–2 s^?1 and k₂ = 2.4 10–2 s^?1.