The effect of mechanical relaxation on ultra-fast charge pulses in flexible epoxy resin nanocomposites

Previously we have reported the existence of small-amplitude charge pulses in crosslinked Polyethylene (XLPE) and epoxy resin with a mobility several orders of magnitude higher than that found for the incoherent charge transport relevant to the steady state current. Here the relationship of this phenomenon to mechanical relaxation in the material is investigated by using a series of epoxy resin nanocomposites based on a resin that has its flexibility increased above that of the fully cured glassy epoxy network by the addition of a suitable flexibilizing chemical. Differential Scanning Calorimetry (DSC) measurements show that the stiffness of the nanocomposite is progressively increased as the nanoparticle concentration increases. Pulsed Electro-Acoustic (PEA) measurements reveal that both positive and negative fast charge pulses exist in the unfilled epoxy at 45 and 70°C under a field of 10?kV/mm with mobility 5×10^?10 to 9×10^?10 m²?V^?1?s^?1, amplitude between 2×10^?5 and 3.6×10^?5 C?m^?2 and repetition rates between 8 and 12?s^?1. These values are reduced progressively as the nanoparticle concentration is increased from 0% in the unfilled epoxy. A???-mode mechanical relaxation is identified in the loss modulus by Dynamical Mechanical Analysis (DMA), whose activation energy moves to higher values with increasing nanoparticle concentration. It is shown that the repetition rates of both positive and negative pulses have similar values and are correlated with the ??-mode activation energy; a similar correlation is found for the activation energy of the mobility of positive pulses. The correlation of the activation energy of the mobility of negative pulses and that of the ??-mode is weaker although both show a progressive increase with nanoparticle concentration. The modification of the fast charge pulse properties by the mechanical stiffness of the epoxy nanocomposite is discussed in terms of the theory presented previously for their formation and transport.     

Linear and nonlinear optical properties of rare earth doped of Ba0.7Sr0.3TiO3 thin films

Ba_0.7Sr_0.3TiO₃:Eu ferroelectric films were deposited on quartz substrates by pulsed laser deposition. The linear absorption coefficient and the linear refractive index calculated from the transmission spectrum at 532 nm were found to be 1.67×10⁴ cm^?1 and 1.82 respectively. The room temperature photoluminescence shows the characteristic emission of Eu³⁺ ions. The nonlinear optical properties of the film were investigated by a single beam Z-scan setup. The negative nonlinear refractive index and two photon absorption coefficient was found to be ?1.508×10^?6 m²/GW and 240 m/GW respectively. The real and imaginary part of the third order susceptibility of the thin films is 2.58×10^?17 m²/V² and 1.16×10^?16 m²/V² respectively. The BST:Eu thin films show good optical limiting property.     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

Magnetic field effects on the hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol as studied by a picosecond laser flash photolysis technique

The hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol at 265 K has been studied with a newly developed picosecond laser flash photolysis apparatus under magnetic fields of 0–1.7 T. The decay rate constant of the radical pair generated was found to increase from 3.42 × 10⁹ s^?1 to 4.15 × 10⁹ s^?1 with increasing the magnetic field from 0 to 1.7 T. The observed magnetic field effects can be explained by the Δg mechanism. Using the simple kinetics model with the Δg mechanism, the rate constant of the escape process from the pair (k _esc) and two rate constants for the T-S spin conversion process (k _T-S) at 0 and 1.7 T were found to be 1.97 × 10⁹ s^?1, 1.45 × 10⁹ s^?1, and 2.12 × 10⁹ s^?1, respectively. From the magnetic field dependence on k _T-S, the difference in the g values of the 4-methoxybenzophenone ketyl and phenylthiyl radicals was estimated to be 0.0087.     

Molecular dynamics simulation of methane in sodium montmorillonite clay hydrates at elevated pressures and temperatures

Computer simulation has been used to study the structure and dynamics of methane in hydrated sodium montmorillonite clays under conditions encountered in sedimentary basins. Systems containing approximately one, two, three and four molecuiar layers of water have followed gradients of 150 bar km^?1 and 30Kkm^?1, to a maximum burial depth of 6 km (900 bar and 460 K). Methane is coordinated to approximately 19 oxygen atoms, of which typically 6 are provided by the clay surface. Only in the three- and four-layer hydrates is methane able to leave the clay surface. Diffusion depends strongly on the porosity (water content) and burial deth self-diffusion coefficients are in the range 0.12 × 10^?9m²S^?1 < D < 12.65 × 10^?9m²s^?1 for water and 0.04 × 10^?9m²s^?1 < D < 8.64 × 10^?9m²s^?1 for methane. Bearing in mind that porosity decreases with burial depth, it is estimated that maximum diffusion occurs at around 3 km. This is in good agreement with the known location of methane reservoirs in sedimentary basins.     

Author index volumes 111–120

Adsorption of monolayer amounts of bismuth on the 100 surface plane of tungsten has been studied by probe hole field emission microscopy and electron spectroscopy. Sub-monolayer bismuth forms a relatively strongly bound layer of bismuth-tungsten dipoles with dipole moment μ = (0.18 ± 0.02) × 10^?30C m and polarizability α = (6.3 ± 1.3) × 10^?40J V^?2m². Changes in work function and their dependence on temperature closely parallel those produced by adsorbed lead which was shown by LEED to form c(2 × 2), p(2 × 2) and (1 × 1) structures. Bismuth is thought to behave in a similar way, but, unlike lead, forms a second monolayer which replicates the first. Electron spectroscopy shows that sub-monolayer bismuth removes the surface state (Swanson) peak and at monolayer coverage a new peak emerges and shifts with increasing coverage. Using Gadzuk's theory, this peak is tentatively attributed to the ²P level in bismuth adatoms which form a p(2 × 2) structure in the first and second monolayers. Its shift with coverage is ascribed to an increase in the local surface field. There remains the difficulty of reconciling the proposed occupation of the ²P level with the observed small positive charge on the bismuth adatom.     

Excess low frequency conduction noise in a granular composite

Granular composites consisting of 25% nickel as 8 nm diameter particles dispersed in an aluminium oxide matrix display excess conduction noise. Co-deposited films with resistance per square about 10⁵ ohms and negative temperature coefficient show a noise power spectral density $\text{S}{}_{\mathrm{v}}\text{(?) =}\text{S}{}_{\mathrm{v}}\text{(1)}\text{?}{}^{\mathrm{\alpha }}$ where α ? 1.10 ± 0.03 over the accessible spectral range of 0.1 Hz ? ? ? 5000 Hz. The amplitude 3 × 10^?15 ? S_v(1) ? 5 × 10^?12 V²Hz^?1, appears to increase approximately quadratically as the applied voltage V_s up to V_s ? 2.5 V and as the first power of V_s for 2.5 ? V_s < 35 V.     

一种测定某些离子导体的导电基本参数的新方法

利用低频交变电场在某些离子导体中能引起偏振态改变的光衍射特性,发展了一种测量这些离子导体的导电基本参数的新方法,并且用它测定了α-LiIO₃单晶的基本离子导电参数,测得其载流子的迁移率激活能E_μ=0.36eV;夫仑克耳缺陷的形成能为E_M=0.59eV;300K时正、负载流子的数密度均为1.6×10¹⁷cm^-3,相对浓度均为1.07×10^-5;当所加电场反平行于晶体的自发极化强 关键词：     

Geometric dynamic recrystallization of austenitic stainless steel through linear plane-strain machining

ABSTRACT

Type 316L austenitic stainless steel was severely plastically deformed at room temperature using linear plane-strain machining in a single pass that imparted shear strains up to 2.2 at strain rates up to 2?×?10³ s^?1. The resulting microstructures exhibited significant grain size refinement and improved mechanical strength where geometric dynamic recrystallization was identified as the primary microstructural recrystallization mechanism active at high strain rates. This mechanism is rarely observed in low to medium stacking fault energy materials. The critical stress required for twin initiation is raised by the combined effects of refined grain size and the increase in stacking fault energy due to the adiabatic heating of the chip, thus permitting geometric dynamic recrystallization. The suppression of martensite formation was observed and is correlated to the significant adiabatic heating and mechanical stabilisation of the austenitic stainless steel. A gradient of the amount of strain induced martensite formed from the surface towards the interior of the chip. As the strain rate is increased from 4?×?10² s^?1–2?×?10³ s^?1, a grain morphology change was observed from a population of grains with a high fraction of irregular shaped grains to one dominated by elongated grain shapes with a microstructure characterised by an enhanced density of intragranular sub-cell structure, serrated grain boundaries, and no observable twins. As strain rates were increased, the combination of reduction in strain induced martensite and non-uniform intragranular strain led to grain softening where a Hall-Petch relationship was observed with a negative strengthening coefficient of ?0.08?MPa m^1/2.     

Measurement of Ar(I) and Ar(II) transition probabilities in LTE ARC plasmas

The transition probabilities of two Ar(I) lines and one Ar(II) line have been measured in emission on wall-stabilized argon arc plasmas (0·5×10⁵?p, Nm^-2?3×10⁵; 10,000?T, K?20,000; 10²²?N_e, m^-3?5×10²³) using the “method of best fit (MBF)”. The results (without line-wing correction) are for Ar(I) at 714·7 nm, A_nm=5·66×10⁵ s^-1±5%; for Ar(I) at 430·0 nm, A_nm=3·40×10⁵ s^-1±5%; for Ar(II) at 480·6 nm, A_nm=8·82×10⁷ s^-1±7%. These values were not influenced by deviations from LTE, which have been observed at electron number densities n_e?10²³ m^-3. The small uncertainties were achieved after careful corrections of different sources of error.     

Electrical transport in ferroelectric Pb[(Fe1/3Sb2/3) x Ti y Zr z ]O3 ceramics

In this article, the studies of the polarization currents and current–voltage characteristics (J–V) are presented. The measurements of the J–V in low and high temperatures as well as at low and high voltages have permitted to recognize certain details of local energy levels in forbidden gap. It has been possible to calculate energy trap levels and their concentration. Calculated trap energy and concentration, under the condition of single trap energy levels, are equal: E _t = 0.55 eV, N _t = 2.97 · 10²³ m^?3 for the sample y = 0.44 and E _t = 0.59 eV, N _t = 1.5 · 10²³ m^?3 for the sample y = 0.47. Knowing the J–V characteristic and the Seebeck coefficient the carriers concentration and their mobility can also be calculated. The carriers concentration and their mobility are equal: n = 3.8 · 10¹⁸ m^?3, µ = 1.4 · 10^?12 m² V^?1 · s^?1 for sample y = 0.44 and n = 6.9 · 10¹⁶ m^?3, µ = 1.3·10^?11 m² V^?1 · s^?1 for the sample y = 0.47.     

Preparation and semiconducting properties of Th3As4

The resistivity, thermoelectric power and Hall constant in the temperature range of 78–830 K were determined for polycrystalline Th₃As₄ samples obtained by annealing thin thorium slabs in arsenic vapour. The samples examined were n-type semiconductors with a carrier concentration ranging from 1.0 × 10¹⁸cm^?3 to 2.8 × 10¹⁸ cm^?3 for which the effective mass was found to be equal to 0.55–0.76m₀. The Hall mobility, about 450cm²V^?1s^?1 at room temperature, obeys a $\text{T}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$ law at high temperatures. On the basis of the electrical measurements the forbidden gap of Th₃As₄ was found to be equal to 0.43 eV.     

Magnetic anisotropy in multilayers

Magnetic anisotropy between in-plane and out of plane magnetic alignments is studied in a variety of multilayer systems using Mössbauer spectrosopy to observe the (Fe) magnetic orientation. The surface anisotropy in Fe/Au (1 1 1) multilayers is measured as K _s = 0.9 × 10^?3 Jm^?2. In Fe/Ni multilayers the dependence of magnetic orientation on external field applied normal to the layers enables volume and interface anisotropies K _v = (?5 ± 1) × 10⁴ Jm^?3 and K _s = (?0.6 ± 0.4)× 10^?3 Jm^?2 to be evaluated. In similar applied field experiments coherent rotation of the magnetic Fe and NiFe layers in Fe/Cu/NiFe/Cu multilayers was observed for intervening Cu layer thickness x = 5 Å but independent rotation for x = 50 Å. Out of plane magnetic components are observed for DyFe₂, YFe₂ thin films and DyFe₂/YFe₂ multilayers. In fields of up to 0.25 T applied inplane only the moments of the YFe₂ film showed significant rotation.     

Lipase catalyzed ultrasonic synthesis of poly-4-hydroxybutyrate-co-6-hydroxyhexanoate

Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50 °C (7.9 × 10^?3 M s^?1), sonic power intensity of 2.6 × 10³ W m^?2 and dissipated energy of 130.4 J ml^?1. Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra? were lower at 2.4 × 10^?4, 1.3 × 10^?4 and 3.5 × 10^?4 M s^?1, respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15 × 10^?3 s^?1 M^?1 for Novozym 435–1.48 × 10^?3 s^?1 M^?1 for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9 × 10³ to 4.5 × 10³ W m^?2 resulted in an increased in acoustic pressure (P_a) from 3.7 × 10⁸ to 5.7 × 10⁸ N m^?2 almost 2.4–3.7 times greater than the acoustic pressure (1.5 × 10⁸ N m^?2) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6 × 10³–1.5 × 10⁴ m s^?2 was calculated i.e. approximately 984–1500 times greater than under the action of gravity.     

Gas mixture effects on ion‐beam flux characteristics from dense plasma focus device: Investigation by the Vlasov–Maxwell equations and experiments

The Vlasov–Maxwell equations were numerically solved to calculate the ion‐beam flux from the plasma of argon and the plasma of mixtures of argon and neon. Some experiments were performed to measure the ion beam from the Amirkabir plasma focus (APF) device. The calculations have shown that the argon ion‐beam flux peaked up to 1.928 × 10³⁰ ions m^?2 s^?1 at the optimum pressure of 1.866 mbar while the neon‐argon mixture's ion‐beam flux reached a maximum of 4.301 × 10³⁰ ions m^?2 s^?1 for 15% neon admixture at the optimum pressure of 1.866 mbar. The calculated kinetic energy of the ion beam has shown a maximum value of 708.7 J for the mixture of 85% argon‐15% neon at the mentioned optimum pressure.     

Diffusion of chromium and manganese in γ-TiAl

The γ-TiAl intermetallic compound with suitable alloying additions has shown considerable promise as a material for high-temperature applications. Diffusion studies in this alloy system are useful in assessment of their creep behaviour and structural stability in service conditions. Tracer diffusion coefficients of ⁵¹Cr and ⁵⁴Mn in a γ-TiAl intermetallic compound containing 54.1 at. % aluminium were determined in the temperature range from 1095 to 1470?K. The temperature dependence of both the diffusing species follows a linear Arrhenius behaviour and can be expressed as D _Cr?=?4.4?×?10^?3exp(?350?kJ?mol^?1/RT)?m^2?s^?1 and D _Mn?=?1.2?×?10^?3?×exp(?326?kJ?mol^?1/RT)?m^2?s^?1. The data are analysed on the basis of empirical correlations between the diffusion and melting parameters applicable for conventional mono-vacancy diffusion mechanism in metals. It is concluded that impurity diffusion in γ-TiAl occurs through the migration of thermal vacancies via nearest-neighbour or next-nearest neighbour jumps.     

Effects of linking chain length and magnetic field on the kinetics of photoprocesses in covalently bonded porphyrin—viologen dyads

The formation and decay kinetics of chain linked triplet radical pairs derived from photo-induced electron transfer reactions in a series of 21 zinc porphyrin-flexible spacer-viologen (ZnP-Sp _n -Vi²⁺) dyads containing 2–138 atoms (n) in the spacer, have been examined by nanosecond laser flash photolysis techniques in an external magnetic field. In non-viscous polar solvents (acetone and CHCl₃ plus CH₃OH = 1:1 v/v), the effect of the spacer length on the rate constant of forward electron transfer can be described by the equation: k _et = k ⁰ _et(n + 6)^?1.5, with k ⁰ _et = 3 × 10¹⁰ s^?1 and 1.2 × 10¹⁰ s^?1 for electron transfer from the singlet and triplet states of ZnP, respectively. In zero magnetic field, the value of the triplet radical pair recombination rate constant, k _r(0) = 0.7 × 10⁶-8 × 10⁶ s^?1, is significantly smaller than k _et. The dependence of k _r(0) on n has an extremum with the maximum near n = 20. In a strong magnetic field (B = 0.21 T), significant retardation of triplet radical pair recombination is observed. In strong magnetic fields the effect of the chain length on triplet radical pair recombination rates is rather small and k _r(B) may vary in the range 0.3 × 10⁶-1 × 10⁷ s^?1. The phenomena observed are discussed in terms of the interplay of molecular and spin dynamics in the limits of slow and fast encounters, taking into account the exchange-interaction.     

X-ray-line plasma satellites of ions in solid target plasmas produced by picosecond laser pulse

The X-ray lines of ions in a solid target interacting with picosecond laser pulses of moderate intensity (2×10¹⁷ W/cm²) were measured on the “Neodim” laser facility. X-ray Ly _α emission spectra of hydrogen-like fluorine ions were observed. Satellite lines were also observed, evidencing the presence of intense plasma oscillations. The positions and separation between the satellites allow their assignment to the intense electrostatic oscillations with an amplitude larger than 10⁸ V/cm and a frequency of about 7× 10¹⁴ s^?1 that is noticeably lower than the laser frequency ω_las～1.8×10¹⁵ s^?1. It is suggested that these oscillations may be due to strong plasma turbulence caused by the development of plasma oscillations of the Bernstein-mode type under the action of a strong magnetic field generated in plasma. The experimental results are compared with the calculated spectra of multicharged ions.     

Anomalous spin-orbit effects in a strained InGaAs/InP quantum well structure

There is currently a large effort to explore spin-orbit effects in semiconductor structures with the ultimate goal of manipulating electron spins with gates. A search for materials with large spin-orbit coupling is therefore important. We report results of a study of spin-orbit effects in a strained InGaAs/InP quantum well. The spin-orbit relaxation time, determined from the weak antilocalization effect, was found to depend nonmonotonically on gate voltage. The spin-orbit scattering rate had a maximum value of 5×10¹⁰ s^?1 at an electron density of n=3×10¹⁵ m^?2. The scattering rate decreased from this for both increasing and decreasing densities. The smallest measured value was approximately 10⁹ s^?1 at an electron concentration of n=6×10¹⁵ m^?2. This behavior could not be explained by either the Rashba or the bulk Dresselhaus mechanisms but is attributed to asymmetry or strain effects at dissimilar quantum well interfaces.