The conductivity properties of protons in ice and mechanism of magnetization of liquid water

From a study of electrical conductivity of protons in the hydrogen-bonded chains in ice we confirm that the magnetization of liquid water is caused by proton transfer in closed hydrogen-bonded chains occurring as a first order phase transition, through which the ice becomes liquid water. We first study the conductive properties of proton transfer along molecular chains in ice crystals in our model. Ice is a typical hydrogen-bonded molecular system, in which the interaction of localized fluctuation of hydrogen ions (H⁺) with deformation of a structure of hydroxyl group (OH) results in soliton motion of the protons along the molecular chains via ionic and bonded defects. We explain further the quantum conductive properties of proton transfer and determine its mobility and conductivity under constant electric-field using a new theory of proton transfer, which agree with experimental values. From features of first order phase-transition for ice, and some experimental data of pure and magnetized water we confirm further that there are not only free water molecules, but also many linear and closed hydrogen-bonded chains consisting of many polarized water-molecules in the liquid water. Thus a ring proton-current, which resembles to a “molecular current” or a “small magnet” in solids, can occur in the closed hydrogen-bond chains under action of an externally applied magnetic field. Then the water molecules in the closed chains can be orderly arrayed due to the magnetic interaction among these ring proton currents and the externally applied magnetic field. This is just the magnetized effect of the water. In such a case the optical and electronic properties of the water, including the dielectric constant, magnetoconductivity, refraction index, Raman and Infrared absorption spectra, are changed. We determine experimentally the properties of the magnetized water which agree with the theoretical results of our model. However, the magnetized effect of water is, in general, very small, and vanishes at temperatures above 100 ^○C.     

Transparent conducting antimony-doped tin oxide films deposited on flexible substrates by r.f. magnetron-sputtering

Transparent conducting antimony-doped tin oxide (SnO₂:Sb) films were deposited on organic substrates by r.f. magnetron-sputtering. Polycrystalline films with a resistivity of ≈ 6.5×10^-3 Ω cm, a carrier concentration of≈ 1.2×10²⁰ cm^-3 and a Hall mobility of ≈ 9.7 cm² v^-1 s^-1 were obtained. The average transmittance of these films reached 85% in the wavelength range of the visible spectrum. Received: 20 April 2001 / Accepted: 23 July 2001 / Published online: 17 October 2001     

Preparation and properties of alumina composites modified by electric field-induced alignment of carbon nanotubes

Catalytic chemical vapor deposition (CVD) grown multi-walled carbon nanotubes (MWNTs) are treated with HF and deionized water and are then placed into alumina ceramics for improvement of both electrical conductivity and mechanical properties. In particular, an alternating current (ac) electric field is applied during the coagulation of the alumina slurries to induce the formation of aligned MWNT networks in the alumina matrix. The coagulated alumina matrix composite bases filled with 2 wt. % ac electric field-induced aligned MWNTs, are then sintered by hot pressing. The electrical conductivities of the prepared composites in directions both parallel and perpendicular to the MWNTs alignment, reach values of 6.2×10^-2 S m^-1 and 6.8×10^-9 S m^-1, respectively, compared with that of 4.5×10^-15 S m^-1 for pristine alumina ceramics. The fracture toughness and flexing strengths of the prepared composites in the two directions are 4.66±0.66 MPa m^0.5, 390±70 MPa, and 3.65±0.46 MPa m^0.5, 191±5 MPa, respectively, compared with 3.78±0.66 MPa m^0.5 and 302±50 MPa for pristine alumina, 4.09±0.15 MPa m^0.5 and 334±60 MPa for alumina filled with 2 wt. % MWNTs prepared without the effect of an electric field, respectively. The results indicate that the electric field leads to anisotropic behaviour. The properties of the composites along the direction of the MWNTs alignment are much improved with the addition of a small amount of CVD grown MWNTs. PACS 61.46.Fg; 61.66.Fn     

Search for solar axions emitted in the M1-transition of 7Li* with Borexino CTF

Results of background measurements with a prototype of the Borexino detector were used to search for 478 keV solar axions emitted in the M1-transitions of ⁷Li^*. The Compton conversion of axion to a photon A+e→e+γ, axioelectric effect A+e+Z→e+Z, decay of axion in two photons A→2γ and Primakoff conversion on nuclei A+Z→γ+Z are considered. The upper limit on constants of interaction of axion with electrons, photons and nucleons – g_Aeg_AN≤(1.0–2.4)×10^-10 at m_A≤450 keV and g_Aγg_AN≤5×10^-9 GeV^-1 at m_A≤10 keV are obtained (90%c.l.). For heavy axions with mass at 100<m_A<400 keV the limits g_Ae<(0.7–2.0)×10^-8 and g_Aγ<10^-9–10^-8 are obtained in assumption that g_AN depends on m_A as for KSVZ axion model. These limits are stronger than obtained in previous laboratory-based experiments using nuclear reactor and artificial radioactive sources. PACS 14.80.Mz; 29.40.Mc; 26.65.+t     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

Proton-conducting hybrid membranes for medium temperature (>100 °C) fuel cells

Hybrid membranes doped with silicotungstic acid (STA) were prepared by sol–gel process with 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phosphoric acid, and tetraethoxysilane as chemical precursors. The thermogravimetry and differential thermal analysis measurements confirmed that the hybrid membranes were thermally stable up to 350 °C. Relatively, a high proton conductivity of 2.85 × 10⁻² S/cm was obtained for 10 mol% STA-doped hybrid membrane at 120 °C under 90% RH. The hydrogen permeability was found to decrease in the temperature range 20–120 °C from 1.64 × 10⁻¹⁰ to 1.36 × 10⁻¹⁰ mol/cm.s.Pa.     

Ionic conductivity studies of chitosan-based polymer electrolytes doped with adipic acid

Chitosan acetate–adipic acid film polymer electrolytes have been prepared by the solution cast technique. The highest conductivity is 1.4 × 10⁻⁹ S cm⁻¹ for 35 wt.% of adipic acid at room temperature. The sample with highest conductivity has the lowest activation energy. Calculations using the Rice and Roth model provide number of mobile ions, η. The conductivity is dependent on the diffusion coefficient and mobility.     

Plasma plume induced during laser ablation of graphite

The plasma plume induced during ArF laser ablation of a graphite target is studied. Velocities of the plasma expansion front are determined by the optical time of flight method. Mass center velocities of the emitting atoms and ions are constant and amount to 1.7×10⁴ and 3.8×10⁴ m s⁻¹, respectively. Higher velocities of ions result probably from their acceleration in electrostatic field created by electron emission prior to ion emission. The emission spectroscopy of the plasma plume is used to determine the electron densities and temperatures at various distances from the target. The electron density is determined from the Stark broadening of the Ca II and Ca I lines. It reaches a maximum of ∼9.5×10²³ m⁻³ 30 ns from the beginning of the laser pulse at the distance of 1.2 mm from the target and next decreases to ∼1.2×10²² m⁻³ at the distance of 7.6 mm from the target. The electron temperature is determined from the ratio of intensities of ionic and atomic lines. Close to the target the electron temperature of ∼30 kK is found but it decreases quickly to 11.5 kK 4 mm from the target.     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

Determination of Enoxacin Using Tb Composite Nanoparticles Sensitized Luminescence Method

In our study, terbium-acetylacetone (Tb-acac) composite nanoparticles have been prepared under vigorous ultrasonic irradiation. The nanoparticles are water soluble, stable and have extremely narrow emission bands and high internal quantum efficiencies. They were used as fluorescence probes in the determination of enoxacin (Enox) based on the fluorescence enhancement of nanoparticles through fluorescence resonance energy transfer (FRET). The influence of buffer solution on the fluorescence intensity was investigated. Under the optimum conditions, the fluorescence intensity of the Tb-acac-Enox system is linearly proportional to the Enox concentration in the Enox concentration range of 2 × 10⁻⁷–1 × 10⁻⁴ M. The correlation coefficient for the calibration curve was 0.9976. The limit of detection as defined by IUPAC, C _LOD = 3S _b/m (where S _b is the standard deviation of the blank signals and m is the slope of the calibration graph) was found to be 3 × 10⁻⁸ M. The relative standard deviation (RSD) for six repeated measurements of 1 × 10⁻⁴ M Enox was 1.35%. The method was applied to the determination of Enox in pharmaceutical formulation and recovery results were obtained from urine samples.     

Conductivity studies of starch-based polymer electrolytes

A proton-conducting polymer electrolyte based on starch and ammonium nitrate (NH₄NO₃) has been prepared through solution casting method. Ionic conductivity for the system was conducted over a wide range of frequency between 50 Hz and 1 MHz and at temperatures between 303 K and 373 K. Impedance analysis shows that sample with 25 wt.% NH₄NO₃ has a smaller bulk resistance (R _b) compared to that of the pure sample. The amount of NH₄NO₃ was found to influence the proton conduction; the highest obtainable room temperature conductivity was 2.83 × 10⁻⁵ S cm⁻¹, while at 100 °C, the conductivity in found to be 2.09 × 10⁻⁴ S cm⁻¹. The dielectric analysis demonstrates a non-Debye behavior. Transport parameters of the samples were calculated using the Rice and Roth model and thus shows that the increase in conductivity is due to the increase in the number of mobile ions.     

Synthesis and characterization of Ag-doped p-type ZnO nanowires

P-type ZnO nanowires with silver (Ag) doping were synthesized via a chemical vapor deposition process. The incorporation of Ag was confirmed by selected-area energy-dispersive x-ray spectroscopy. The formation of acceptor states was demonstrated by temperature and excitation power-dependent photoluminescence measurements. Characterization of field-effect transistors using Ag-doped ZnO nanowires as channels showed p-type conductivity of the nanowires with a hole concentration of 4.9×10¹⁷ cm⁻³ and a carrier mobility of approximately 0.18 cm² V⁻¹ s⁻¹.     

Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol

An attempt has been made to prepare a new proton conducting polymer electrolyte based on polyvinyl alcohol (PVA) doped with NH₄NO₃ by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared polymer electrolyte has been found by ac impedance spectroscopic analysis. The highest ionic conductivity has been found to be 7.5 × 10⁻³ Scm⁻¹ at ambient temperature for 20 mol% NH₄NO₃-doped PVA with low activation energy (~0.19 eV). The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship, which shows hopping of ions in the polymer matrix.     

Preparation and characterization of polyindole–ZnO composite polymer electrolyte with LiClO<Subscript>4</Subscript>

This paper describes the preparation and conductivity studies of polyindole–ZnO composite polymer electrolyte (CPE) with LiClO₄. Polyindole–ZnO-based polymer nanocomposites were prepared by chemical method and characterized by XRD, infrared (IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The IR spectrum confirms the intermolecular interaction between polyindole and ZnO. The significant spectral changes of polyindole and ZnO nancomposites reveal the strong interaction between polyindole and ZnO nanoparticles. The structural morphologies of the ZnO, polyindole, and polyindole–ZnO are obtained from SEM. The TEM image of polyindole nanocomposite shows that ZnO is embedded in polyindole matrix. An enhanced conductivity of 4.405 × 10⁻⁷ S cm⁻¹ at 50 °C for the CPE was determined from impedance studies.     

Three-body decay of a rubidium Bose–Einstein condensate

We have measured the three-body decay of a Bose–Einstein condensate of rubidium (⁸⁷Rb) atoms prepared in the doubly polarized ground state F=m _F =2. Our data are taken for a peak atomic density in the condensate varying between 2×10¹⁴ cm^-3 at initial time and 7×10¹³ cm^-3, 16 s later. Taking into account the influence of the uncondensed atoms on the decay of the condensate, we deduce a rate constant for condensed atoms L=1.8 (±0.5) ×10^-29 cm⁶ s^-1. For these densities we did not find a significant contribution of two-body processes such as spin dipole relaxation. Received: 24 November 1998 / Revised version: 26 June 1999 / Published online: 8 September 1999     

A comparative study of lithium and sodium salts in PAN-based ion conducting polymer electrolytes

The conducting polymer electrolyte films consisting of polyacrylonitrile (PAN) as the host polymer, lithium triflate (LiCF₃SO₃) and sodium triflate (NaCF₃SO₃) as inorganic salts were prepared by the solution-cast technique. The pure PAN film was prepared as a reference. The ionic conductivity for the films is characterized using impedance spectroscopy. The room temperature conductivity for the PAN + 26 wt.% LiCF₃SO₃ film and the PAN + 24 wt.% NaCF₃SO₃ film is 3.04 × 10⁻⁴ S cm⁻¹ and 7.13 × 10⁻⁴ S cm⁻¹, respectively. XRD studies show that the complexation that has occurred in the PAN containing salt films and complexes formed are amorphous. The FTIR spectra results confirmed the complexation has taken place between the salt and the polymer. These results correspond with surface morphology images obtained from SEM analysis. The conductivity–temperature dependence of the highest conducting film from PAN + LiCF₃SO₃ and PAN + NaCF₃SO₃ systems follows Arrhenius equation in the temperature range of 303 to 353 K. The PAN containing 24 wt.% LiCF₃SO₃ film has a higher ionic conductivity and lower activation energy compared to the PAN containing 26 wt.%LiCF₃SO₃ film. These results can be explained based on the Lewis acidity of the alkali ions, i.e., the interaction between Li⁺ ion and the nitrogen atom of PAN is stronger than that of Na⁺ ion.     

Soliton patterns and breakup thresholds in hydrogen-bonded chains

The dynamics of protons in hydrogen-bonded quasi one-dimensional networks are studied using a diatomic lattice model of protons and heavy ions including a φ⁴ on-site substrate potential. It is shows that the model with linear and nonlinear coupling of the quartic type between lattice sites for the protons admits a richer dynamics that cannot be produced with linear couplings alone. Depending on two types of physical boundary conditions, namely of the drop or condensate type, and on conditions requiring the presence of linear and nonlinear dispersion terms, soliton patterns of compact support, whether with a peak, drop, bell, cusp, shock, kink, bubble or loop structure, are obtained within a continuum approximation. Phase trajectories as well as analytical studies provide information on the disintegration of soliton patterns upon reaching some critical values of the lattice parameters. The total energies of soliton patterns are computed exactly in the continuum limit. We also show that when anharmonic interactions of the phonon are taken into account, the width and energy of soliton patterns are in qualitative agreement with experimental data.     

Electronic band structures of low-dimensional adsorbate systems: Rare-gas adsorption on transition metals

Angle-resolved photoemission data are dis-cussed for five different Xe adlayers which exhibit electronic structures of different dimensionalities. Xe adsorption on Ni (110)-(1 × 2)-3Hand the (×) R30^° Xe layer on Ru (001) reveal two-dimensional (2D) Xe-derived band structures that are characteristic for hexagonal rare-gas layers. Different Xe 5p dispersion widths on Ni and on Ru are found due to the difference in the Xe-Xe nearest-neighbor distance. For three rare-gas systems (two different Xe coverages on hydrogen-modified Pt (110)-(1 × 2)-H and Kr step decoration on a Pt (997) surface) true one-dimensional (1D) band structures are found. For Xe step adsorption on Pt (997), electronic localized (0D) behavior is observed due to an enlarged Xe-Xe separation. The qualitative differences of the band structures in the case of 2D, 1D and 0D rare-gas systems are demonstrated and are explained by the different dimensionalities of the various structures. Received: 3 August 2000 / Accepted: 4 August 2000 / Published online: 7 March 2001     

Role of an acceptor impurity in the proton transfer in proton-conducting oxides

The influence of interaction of protons with defects (acceptor impurities, oxygen vacancies) and with each other on the proton transfer in acceptor-doped proton-conducting oxides A ^II B _1?x ^IV R _x ^III O_{3 ? δ} with the perovskite structure and in oxides A _2?x ^III R _x ^II O_{3 ? δ} with the structure of a distorted fluorite (bixbyite) has been investigated theoretically. The tracer diffusion coefficient D* and proton mobility have been calculated by the Monte Carlo method and analytically. It has been shown that the interaction of protons with defects substantially affects the magnitude and behavior of the transfer coefficients. The interaction with acceptor impurities plays the most important role. The proton mobility significantly decreases even at a low dopant concentration (x ～ 1–3 at %). The dependence of the proton conductivity σ on the impurity concentration can exhibit maxima. For oxides with the bixbyite structure including nonequivalent cation sites, the distribution of the dopant over these sites has a strong influence on the dependence σ(x). The obtained results have been used to interpret the experimental data on the proton conductivity for a number of oxides.     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk