Doping of polyacetylene by diffusion of iodine

The solubility limit and diffusion coefficient of I₂ in (CH)_x polymer have been measured with a radiotracer technique. The concentration of iodine in the polymer is a function of the surrounding concentration outside the film at equilibrium (free enthalpy of solubility = ? 0.20 eV). The data are consistent with the following mechanism: liquid state diffusion of the solution in between the fibrils and solid state diffusion of iodine inside the fibrils. The macroscopic diffusion coefficient throughout the film is equal to 10^?9cm²sec^?1. These results restrict the present (CH)_x polymer to heterolithic device applications after encapsulation. Monolithic substrate application will require a further inhibition of diffusion.     

Kinetics of decomposition of the solid electrolyte RbCu4Cl3I2

The processes of electrochemical decomposition of the solid electrolyte RbCu₄Cl₃I₂ at the vitreous carbon electrode and chemical decomposition of RbCu₄Cl₃I₂ by iodine has been investigated. The anodic decomposition of the electrolyte occurs in two steps. At first, the oxidizing electrode reaction of Cu⁺ ions up to Cu²⁺ ions takes place at potentials higher than 0.57 V and onto the electrode surface the layer of decomposition products is formed, including the compound of divalent copper RbCuCl₃. Then the oxidizing reaction of I ions occurs at potentials higher than approximately 0.67 V with deposition of the iodine layer onto the electrode surface. The deposition rate of the layers of decomposition products is controlled by instantaneous nucleation and two-dimensional growth of the deposit. It was shown that slow diffusion of the iodine in the reaction product layer is a limiting step in the chemical interaction of iodine with RbCu₄Cl₃I₂. For the compressed RbCu₄Cl₃I₂ sample investigated, iodine diffusion coefficient was calculated to be 6.2×10⁻⁷ cm² s⁻¹. Iodine loss from the glassy carbon surface is about 1.1×10⁻⁴ g cm⁻² s⁻¹ at the thickness of the RbCu₄Cl₃I₂ sample is equal to 2 mm.     

Erbium incorporation in LiNbO3 by diffusion-doping

 The erbium incorporation into LiNbO₃ by diffusion doping is investigated in detail by means of Secondary Ion Mass Spectrometry, Secondary Neutral Mass Spectrometry, Rutherford Backscattering, Atomic Force Microscopy, X-ray Standing Wave technique and optical site-selective spectroscopy. The diffusion of erbium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient. The diffusion constants and activation energies for Z-cut (X-cut) LiNbO₃ are 4.8×10^-5 cm²/s (12.0×10^-5 cm²/s) and 2.28 eV (2.44 eV), respectively. A limited solubility of erbium in LiNbO₃ has to be taken into account increasing exponentially with rising temperature. During the first step of diffusion an Er _x Nb _y -oxide layer is formed at the surface of the sample acting as diffusion reservoir. Erbium is incorporated into LiNbO₃ on vacant Li-sites slightly shifted from the original Li-position along the (-c)-direction. Site-selective spectroscopy found four distinguishable energetically different erbium centres at this lattice site resulting from locally different symmetries of the crystal field. Received: 21 March 1996 / Accepted: 12 August 1996     

Determination of parameters of Cu surface mass transport on sapphire from morphological changes of beaded films caused by evaporation

s , the surface diffusion coefficient, D_s ^′, and the surface reaction rate coefficient, β_s ^′, of Cu on alumina are determined in the temperature range 1048–1198 K. Measuring simultaneously the time dependence of the effective thickness, H_eff(t), the lateral shift of the boundary, y(t) of beaded films (BF) and using vapour pressure data we concluded that the process is controlled by surface reaction at the perimeters of beads. Supposing Arrhenius-type temperature dependence for D_s ^′, β_s ^′ and λ_s the activation energies and preexponential factors have been calculated. Received: 2 October 1996/Accepted: 27 November 1996     

Kinetics of the sorption of <Superscript>3</Superscript>He by C<Subscript>60</Subscript> fullerite. The quantum diffusion of <Superscript>3</Superscript>He and <Superscript>4</Superscript>He in fullerite

The kinetics of the sorption and subsequent desorption of gaseous ³He in a C₆₀ fullerite powder has been studied in the temperature range of 2–292 K. The temperature dependences of the diffusion coefficients of ³He and ⁴He impurities in fullerite have been plotted using the measured characteristic times of filling of octahedral and tetrahedral interstices, as well as previous data. These temperature dependences of the diffusion coefficients of ³He and ⁴He impurities in fullerite are qualitatively similar. A decrease in the temperature from 292 to 79 K is accompanied by a decrease in the diffusion coefficients, which corresponds to the dominance of the thermally activated diffusion of helium isotopes in fullerite. A further decrease in the temperature to 8–10 K leads to an increase in the diffusion coefficients by more than an order of magnitude. The diffusion coefficients of ³He and ⁴He are independent of the temperature below 8 K, indicating the tunnel character of the diffusion of helium in C₆₀ fullerite. The isotope effect is manifested in the difference between the absolute values of the diffusion coefficients of ³He and ⁴He atoms at the same temperatures.     

An electrochemical study of copper diffusion in non-stoichiometric copper sulphide

The diffusion of copper in hexagonal chalcocite (Cu₂S) is not very well-known. In this work electrochemical cells with natural polycrystalline chalcocite working electrodes have been studied by electrochemical impedance spectroscopy (EIS) over a large frequency range at equilibrium potential. To study this phenomenon between 120 and 160°C a solid electrolyte RbCu₄Cl₅ has been used. The impedance spectra present two distinct regions. At high frequencies the general shape of the diagram in the Nyquist plane is a depleted are of a circle. Changes in electrolyte resistance, interfacial capacitance and transfer resistance have been studied as a function of temperature. At low frequencies, a diffusion impedance is observed attributed to the mobility of copper vacancies. Diffusion coefficients, with an activation energy of 1.7 eV, have been deduced from the impedance diagrams (4.7·10⁻⁵cm² s⁻¹ at 130°C). These results are compared with those obtained with orthorhombic chalcocite between 30 and 60 °C by EIS and using an electrochemical cell with a cupric liquid electrolyte. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Sorption and diffusion behaviours of strontium in sodium-type bentonite bed

Sorption and diffusion of Sr were examined using a typical Japanese bentonite. The experimental results showed that Sr sorption on the bentonite had linear relationship between the equilibrium Sr concentration and Sr sorption amount, i.e., Henry’s type of sorption, in wide initial Sr concentration from 1.1×10⁻⁹ to 1.1×10⁻⁴ mol L⁻¹ at pH 10. The Sr sorption also indicated pH dependence in pH range between 2 and 12. Sorption modelling calculation indicated that cation-exchange reactions contributed to Sr sorption in the pH range studied and a surface complexation reaction was predominant above pH 8. Diffusion of Sr in loosely compacted bentonite bed was described by pore and surface diffusion and surface complexation of Sr. Chemical-transport calculations reproduce the diffusion data at pH 5 using the cation-exchange parameters obtained in the analysis of the batch sorption experiment.     

Kinetics and equilibrium adsorption of nano-TiO2 particles on synthetic biofilm

Understanding the environmental behavior of nanoparticles includes their interaction with biofilms, which is a covering on the surface of a living or nonliving substrate composed of microorganisms. This study focuses on nano-TiO₂ sorption mechanism by synthetic biofilm that was prepared as superporous spherical beads from agarose, using batch stirred flasks kept at room temperature. The pH plays an important part in these phenomena, by its influence on the nanoparticles and biofilm chemistry, where the biofilm nanoTiO₂ uptake at neutral pH was enhanced over acidic conditions. Hydroxylation of TiO₂ nanoparticles, dependent on pH and the salinity of the solution, influences the stability of colloids, the sorption kinetics via the nature of limiting phases: diffusion through the boundary layer or intrabiofilm mass transfer and the sorption mechanism. The sorption follows pseudo first-order adsorption kinetics with estimated average rate constants of 2.2 (min^? 1). Equilibrium isotherms were evaluated using Langmuir and Freundlich isotherms to obtain the maximum uptake at different solution pH and the free energy of the adsorption. The adsorption is apparently irreversible because biofilm limits diffusion of particles out of the pores and the complexation active binding sites on the surface hydrated biofilm to the hydrophilic TiO₂ nanoparticles.     

Saturated absorption experiments using a free running CW dye laser

The hyperfine structure of some new iodine lines has been observed over the tuning range of Rhodamine 6G (5800–6200 Å), using a free running, single mode cw dye laser. The resolution obtained in this experiment allowed to calculate the hyperfine constants of the excited state (³π₀⁺) of iodine with an accuracy of 2% for the quadrupole coupling constant and 50% for the magnetic one.     

Study of cesium sorption on Na and Ca-Mg bentonites using batch and diffusion experiments

In this study the cesium sorption on two different bentonites (Ca-Mg bentonite Rokle and Na bentonite Volclay KWK 20–80) has been compared using two different experimental approaches — batch and diffusion methods. The distribution coefficients (K_ds) calculated for variable liquid-to-solid ratio (batch) and dry density (diffusion) were evaluated with respect to the main uncertainties affecting both approaches. It has been concluded that there are significant differences between selected bentonites in mineral composition, cation exchange capacity (CEC) and sorption characteristics. The K_d values calculated from batch sorption and diffusion data were found comparable only for Na bentonite Volclay KWK 20–80. The considerably higher sorption of Cs on Ca-Mg bentonite Rokle was explained by its higher content of cesium-selective sorbents (illite, vermiculite).     

Synthesis,spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[(<Emphasis Type="Italic">E</Emphasis>)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[(E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I₂), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and ¹H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I₂)] (1), [(Schiff)(Br₂)] complexes with a ratio of 1:1 and [(Schiff)(PiA)₃] complexes with 1:3 have been prepared. In the picric acid complex, infrared and ¹H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff⁺, I₂^∙−] and [Schiff⁺, Br₂^∙−], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats–Redfern and Horowitz–Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.     

Low contact resistance of n+-Si/Ti/WNx/Al submicron contact structures

+ -Si/Ti/WN_x/Al multi-layer metallization scheme. The contact resistance has been strongly related to the plasma nitridation of the Ti surface because the contact resistance of n⁺-Si/Ti/WN_x/Al with contact size of 0.49 μm² about 100–130 Ω, whereas without the nitridation of the Ti surface the contact resistance rises up to 200–390 Ω. ¹⁹F (p,αγ) nuclear resonance analysis and Auger electron spectroscopy reveal that F adatoms on the Ti surface are successfully removed by the 30 s nitridation and as a result, the low contact resistance can be achieved. Received: 16 July 1996/Accepted: 5 November 1996     

Polarized fluorescence of jet-cooled molecular iodine

The degree of polarized fluorescence of molecular iodine ¹²⁷I₂ cooled in a supersonic jet under rotationally selective excitation in the electronic transition B ³Π_0u ⁺-X ¹Σ _g ⁺ has been measured and calculated. It was found that the interaction of the angular momentum of the molecule with the nuclear spins of iodine atoms leads to a considerable depolarizing effect. This effect is most pronounced for small rotational quantum numbers of the angular momentum that are comparable with the total nuclear spin of the iodine molecule, which is equal to 5.     

The vacuum ultraviolet spectrum of krypton and xenon excimers excited in a cooled dc discharge

u , 0_u ⁺ and the weakly bound ground state 0_g ⁺. A semiempirical method was suggested and applied to describe the experimental spectra and to estimate the temperature of the radiating plasma volume. Electron impact, transferring dimers from the ground state to the excited states, is shown to be an efficient excitation mechanism in the 100–850 hPa and the 10–50 mA pressure and discharge current ranges. The spectra obtained as well as the results of calculations corroborate the high rate of this mechanism. Received: 31 July 1996/Revised version: 17 March 1997     

Diffusion of deuterium in tantalum from internal friction measurements (Gorsky effect)

The long-range diffusion of deuterium in tantalum has been investigated as a function of temperature by means of the anelastic process due to redistribution of deuterium impurities between compressed and dilated regions of the sample, under an applied stress alternating at about 4 Hz. The diffusion coefficient was found to obey an Arrhenius-type law in the temperature range 200–390 K; a deviation was observed at lower temperatures. The diffusion parameters in the exponential region areD _0D=(3.3±1.5)×10⁻⁴ cm²/s, andW _D=(0.176±0.008) eV.     

Influence of pressure on ionic transport in amorphous electrolytes: Comparison between glasses and salt polymer complexes

Accurate conductivity measurements as a function of hydrostatic pressure (1 – 5000 bars) and temperature (20 – 150 °C) have been performed on a cationic inorganic glass and a cationic conducting polymer. In both cases, the conductivity decreases with increasing pressure and the variation of Inσ at constant temperature as a function of pressure gives straight lines with slopes which allow an “activation volume”, ΔV*, to be obtained by the relationship (∂lnσ/∂P)_T=− (ΔV*/RT). In the case of silver metaphosphate glass, studied below its glass transition temperature, the activation volume (5 cm³⋅mol⁻¹) is temperature independent and equal to the molar volume of the silver cation. Since the transport mechanism implies a free energy barrier, this volume is a real activation volume, corresponding to the difference in volume between a mole of the moving species in its activated transition state and its volume at normal equilibrium. In the case of the sodium conductive polymer, studied above its glass transition temperature, the previous thermodynamic definition does not hold any more because the ionic transport follows a V.T.F. behaviour rather than an Arrhenius law. Consequently, ΔV* is an “apparent activation volume” without a simple physical meaning. Experimental values are higher (20 to 30 cm³⋅mol⁻¹) and decrease with temperature. In this polymer, the mobility of the charge carriers is interpreted in terms of free volume mechanism. From the variations of the apparent activation volume with temperature, the critical free volume V_f* for an elementary displacement is estimated. For the Na⁺ conductive ionomer V_f* is estimated to be equal to 13 cm³⋅mol⁻¹. This large value would indicate the participation of macromolecular chain segments in the ionic transport. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Grain boundary diffusion of Cu in TiN film by X-ray photoelectron spectroscopy

In this study, the grain boundary diffusion of Cu through a TiN layer with columnar structure was investigated by X-ray photoelectron spectroscopy (XPS). It was observed that Cu atoms diffuse from the Cu layer to the surface along the grain boundaries in the TiN layer at elevated temperature. In order to estimate the grain boundary diffusion constants, we used the surface accumulation method. The diffusivity of Cu through TiN layer with columnar structure from 400 °C to 650 °C is D_b≈6×10⁻¹¹exp(−0.29/(k_BT )) cm²/s. Received: 18 May 1999 / Accepted: 8 September 1999 / Published online: 23 February 2000     

In search of photon’s elementary axial magnetostatic field

 Experimental investigations of the photon’s B ⁽³⁾-field (third longitudinal polarization) are reported. The existence of an “axial magnetostatic field of photon” has been predicted in B _π or B ⁽³⁾-theory as the fundamental property of the circularly polarized light, and reported in numerous papers and monographs. High-sensitivity detection has been employed in photomagnetic induction, Faraday, and inverse Faraday effects (IFE) originating from such a field. The results of all three experiments clearly disprove the claims of B _π-theory. Putting together these results and theoretical calculations in perspective, it is concluded that such fields are non-existent. Received: 25 January 1996 / Revised version: 24 May 1996     

Nanotechnology studies of layered fluoride superionic conductors

A computer simulation by a molecular dynamics method at constant volume has been performed on a model material that is composed of accumulating two different fluoride conductors: ⋯BaF₂–CaF₂–BaF₂–CaF₂⋯. The average value of CaF₂ and BaF₂ for the lattice constant of the new layered material is prepared to hold its mechanical strength. The CaF₂ region is compressed and the BaF₂ region is stretched along the c axis (z axis) in the thermal equilibrium state. It is obtained that the diffusion coefficient and ionic conductivity of F− ions in the layered fluoride conductors increases with decreasing periods, more specifically with the number of interfaces. The layer depth dependence on transport coefficients approximately coincides with the experiment.     

Multi-wavelength excimer ultraviolet sources from a mixture of krypton and iodine in a dielectric barrier discharge

New ultraviolet (UV) sources (excimer lamps) have been demonstrated using mixtures of krypton and iodine in a high-pressure dielectric barrier discharge to provide intense multi-wavelength radiation at λ=183 nm (atomic iodine line, ⁴ P _5/2?² P _3/2), 191 nm (KrI^*, B _1/2?X _1/2), 206 nm (atomic iodine line, ² P _3/2?² P _1/2), and 342 nm (I^* ₂, D _1/2?X _1/2). The characteristics of the optical emission spectra of the atomic species and the excited dimers (excimers) formed for different total gas pressures and in the presence of a buffer gas have been investigated. The highest intensity, at 183 nm, is obtained at pressures up to 1 bar while the overall emission spectra can be controlled by adjusting the total pressure. The results show that these strong multi-wavelength lamps offer an interesting alternative to conventional UV sources. Received: 1 March 2000 / Revised version: 5 April 2000 / Published online: 30 June 2000