Doping mechanism of a conducting polymer: Iodine-doped polyacetylene

We have achieved a technique for determining the diffusion profiles of impurities in the polymers by using a radio-tracer and a microslicing method. We describe the diffusion profiles of iodine in polyacetylene in the temperature range ?60 +20°C. The results show that: (1) iodine penetrates through the interfibril spaces; (2) there is a simultaneous chemical reaction of the first order on the fibrils between polyacetylene and iodine. When the dopant is in solution in pentane, the liquid state interfibril diffusion obeys the Arrhenius law: D = 1.73 × 10^?3 exp[$\text{?0.122(eV)}\text{kT}$] cm² · sec^?1. The kinetic constant of the reaction obeys the similar equation: k = 0.754 exp[$\text{?0.0867(eV)}\text{kT}$] sec^?1.     

Composition dependence of the ionic diffusion coefficients in yttria-stabilized zirconias

The diffusion coefficient of the O²⁻ ions in yttria-stabilized zirconia (1−x)ZrO₂·xYO_1.5 has been investigated as a function of the concentration of Y³⁺ ion over a range x = 0.131–0.261 by using quasielastic light scattering. The diffusion coefficients were deduced from the analysis of the temperature dependence of the scattering intensity at 3 GHz. It is concluded that the diffusion coefficient reaches its maximum value at x = 0.165. The composition dependence of the scattering intensity suggests that the concentration of the moving carrier decreases as the Y³⁺ content increases in spite of an increase of the oxygen vacancies.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

Structural relaxation in the CoP-CoNiP system upon low-temperature annealing

The atomic structure of alloys in the CoP-CoNiP system in the initial state and its behavior upon low-temperature annealing is investigated. It is shown that structural relaxation starts at temperatures of 150–200°C and results in local atomic ordering at the network boundaries. Crystals 2–5 nm in size start to undergo nucleation at the boundaries of structural heterogeneities when heated further to 250–300°C. The nanocrystal structure corresponds to the metastable phase delta-Co (ICSD 42684) and the unknown phase Co_{1 ? x} P _x . The estimated diffusion coefficient for CoP alloy is 10^?14 m² s^?1, according to the experimental data.     

Iodine as a donor in CdS

Iodine doped single crystals of CdS were grown from the vapor phase. High temperature Hall effect measurements for the crystals equilibrated with Cd and S₂ vapors at temperatures between 700 and 1000°C gave the free electron concentration as a function of p_Cd or p_S2 and temperature. The results can be explained on the basis of a model in which the CdS is saturated with iodine at low p_Cd (=high p_S2) but unsaturated at high p_Cd.The solubility of iodine in CdS is given by c_t=1·73×10²²p_S2^?1/8 exp (?1·045 eV/kT) cm^?3 atm^?1/8=4·62×10¹⁹p_Cd^1/4 exp (?0·195 eV/kT) cm^?3 atm^1/4The formation of pairs (I_SV_Cd)′ from I_S^· and V_Cd″ is governed by the equilibrium constant K_{P(I, V)}=4 exp (≤1·1 eV/kT)If Cd diffusion occurs primarily by free vacancies, the Cd^* tracer self diffusion leads to a vacancy mobility of (1·2±0·5)×10^?5 cm² sec^?1 at 900°C, in agreement with results reported by Woodbury [12], but (7±3) times larger than reported by Kumar and Kroger [10].     

The relationship between chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice

The theoretical model developed by Lidiard was extended to describe the relationship between the chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice.It is shown that the relationship between the chemical diffusion coefficient, D, and the tracer diffusion coefficient, D¹, is D = 2D¹ if the migration of dimers is the principal mechanism of transport and for the migration of trimers D = 3D¹ if the concentration of impurity ion is relatively small. These relationships are valid regardless of the charge of the aliovalent or lattice ions.The chemical diffusion coefficients of Cr³⁺ in Cr-doped MgO were determined for three different temperatures, 1656, 1717 and 1768K, and for the concentration region 2.5×10^?2?2.8×10^?1 mole% Cr₂O₃. Using previously determined values for the tracer diffusion coefficient of ⁵¹Cr in Cr-doped MgO it was found that for the temperature and concentration region investigated D = (2.00±0.17)D¹ which indicates that diffusion proceeds primarily by the migration of dimers.     

Spectral and nonlinear studies of an aniline blue dye in liquid and solid media

Solid-state dye-doped polymers are an attractive alternative to conventional liquid dye solutions. In this paper, the spectral characteristics and nonlinear properties of the Aniline Blue dye has been studied. The third-order nonlinear optical properties of the Aniline Blue dye in ethanol and a dye-doped polymer film were measured by the Z-scan technique using a 632.8-nm He-Ne laser. This material exhibits a negative optical non-linearity. The dye at a 0.4-mM concentration exhibited a nonlinear refractive coefficient (n ₂ = ?4.02 × 10^?8 and ?4.41 × 10^?8 cm²/W in liquid and solid media, respectively), a nonlinear absorption coefficient (β = ?9.7 × 10^?4 and ?11.63 × 10^?4 cm/W in liquid and solid media, respectively), and susceptibility (x ⁽³⁾ = 1.844 × 10^?6 and 2.028 × 10^?6 esu in liquid and solid media, respectively). These results show that the Aniline Blue dye has potential applications in nonlinear optics.     

The defect structure of silver-doped CdS

High-temperature Hall effect measurements are carried out on CdS doped with 2·5 × 10¹⁷?2·3 × 10²⁰ Ag cm^?3 under various cadmium and sulfur pressures. At high p_cd and low silver concentrations, Ag acts as a donor. At higher concentrations self compensation occurs. An anomalous variation of the Hall coefficient with p_s2 indicates that the electron concentration increases with increasing p_s2. This is attributed to the formation of anti structure defects S_cd. A complete defect model is proposed, and published solubility and diffusion data for Ag in CdS in equilibrium with (Ag, Cd) alloys are reinterpreted on the basis of this model.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

An investigation of lithium transport properties in V6O13 single crystals

Lithium has been incorporated into single crystals of V₆O₁₃ by coulometric titration in solid state electrochemical cells. A single phase region was identified for Li_xV₆O₁₃ between x=0 and x=0.17 at 120°C. The lithium chemical diffusion coefficient, self-diffusion coefficient, ionic conductivity and partial molar entropy have been estimated at intervals over this composition range in two specific crystallographic directions. The chemical diffusion coefficients were found to be constant in a particular crystal direction with values of 3.5 × 10^-8 cm² s^-1 and 4.9 × 10^-9 cm² s^-1 perpendicular to the (0 1 0) and (0 0 1) planes respectively.     

Homogeneity examination of a disordered magnetic alloy by means of CEMS

The depth sensitivity of the Mössbauer effect conversion electron spectroscopy (CEMS) offers a possibility to check the homogeneity of an alloy as a function of the sample thickness. We present experimental results on (Fe_0.65Ni_0.35)_1-xMn_x (x=0.026) prepared by diffusion of Mn into a Fe_0.65Ni_0.35 foil. On an inhomogeneous sample we determined the diffusion coefficient of Mn in Fe_0.65Ni_0.35 at 1300 K to be about 10^?11 cm²/s.     

Diffusion and NMR spin lattice relaxation of 1H in α′ TaHx and NbHx

The concentration and temperature dependence of the self diffusion coefficient, D, of H in Group V transition metals Nb and Ta has been measured for the α^' phase. The nuclear magnetic resonance spin lattice relaxation time, T₁, was measured in Ta only. A pulsed field gradient, NMR spin echo technique was utilized to measure D. In both systems, the activation energy increases with hydrogen concentration while the pre-exponential factor is not strongly concentration dependent. The diffusion results are compared with published values of the macroscopic diffusion coefficient, $\text{D}{}^1$, obtained from Gorsky effect measurements. Values of the thermodynamic factor [$\text{(}\text{ρ}\text{kT}\text{)(}\text{?μ}\text{(?ρ)}$] are found for selected ρ and T, where μ is the chemical potential and ρ is the density of hydrogen atoms. These values agree with known determinations of the same factor obtained from the Gorsky effect relaxation strengths, but the agreement with results from solubility measurements is less satisfactory. NMR relaxation is partitioned into conduction electron (T^?1_1e) and dipolar (T^?1_1d) relaxation rates. The observed x dependence of ($\text{D}\text{T}{}_{\mathrm{1d}}$) is inconsistent with random occupancy of tetrahedral sites, and it is suggested that a repulsive interaction exists between H atoms on nearest neighbor sites.     

An electrochemical study on the substituted spinel LiMn1.95Cr0.05O4

Cyclic voltammetry, galvanostatic charge?Cdischarge technique, potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS) were used to study the behavior of a LiMn_1.95Cr_0.05O₄ (substituted lithium?Cmanganese spinel) electrode in nonaqueous electrolytes at 25 °C. Quantitative and qualitative changes of the electrode transport parameters as functions of lithium concentration were analyzed. Several equivalent circuits are discussed; the results obtained by different methods are compared. The PITT and EIS results are in good agreement; the chemical diffusion coefficient D varies within 10^?14?C10^?9 cm² s^?1 depending on the lithium content in the Li_xMn_1.95Cr_0.05O₄ electrode.     

Cation distribution of the system Zn1−xCoxFeMnO4 by x-ray,electrical conductivity and Mössbauer studies

Structural, electrical and Mössbauer studies were carried out for the system Zn_1?xCo _x Fe MnO₄. It is observed that forx?0.6, the ionic configuration of the system is Zn _1?x ²⁺ Mn _x ²⁺ [Co _x ³⁺ Mn _1?x ³⁺ Fe³⁺]O ₄ ^2? and forx?0.8 Fe³⁺ ions occupy tetrahedral site also. On the basis of electrical and Mössbauer studies a probable valence distribution of CoMnFeO₄ has been suggested. All the compounds showed positive values of thermoelectric coefficient and electrical conduction takes place by a hopping mechanism. Activation energy and thermoelectric coefficient values decreased with decrease in concentration of Zn²⁺ ions. The compounds possess low mobility values varying between 10^?7 and 10^?9 cm²/V sec.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Mass transport in cuprous oxide

The chemical diffusion coefficient of Cu₂O has been obtained for an oxygen partial pressure near 5 10^?4 atm as a function of the temperature in the range 700–900°C D? = 1 62 10^?4 exp(?5140 ± 600 cal mol ^?1)/RT cm²s^?1 This was easily achieved according to the electrochemical method used for the preparation of gaseous mixtures whose Po₂; is lower than 10^?5 atm The slight difference observed with the previously published results by Maluenda, and obtained for Po₂ values which increase with T between 10^?4 and 0.21 atm, may be due to an oxygen partial pressure effect already observed in the case of CoO. An ambipolar treatment of the chemical diffusion, in the case of p-type semiconductor M_aO_b, oxides, has allowed us to express the chemical diffusion coefficient as a function of the concentration of the prevailing defects and of their diffusion coefficient In the case where the prevailing defects are cationic vacancies α times ionized we have shown that the expression D? = (1 + α)D_vα can be generalized to the A₂O compounds This set of results has allowed us, according to the copper self diffusion data obtained recently by Peterson etal, to estimate the apparent enthalpy of formation of the catiomc vacancies ΔH_f 23 ± 0 8 kcal mol^?1.     

Preparation and ionic conductivity of composite polymer electrolytes based on hyperbranched star polymer

Hyperbranched star polymer HBPS-(PPEGMA) _x was synthesized by atom transfer radical polymerization (ATRP) using hyperbranched polystyrene (HBPS) as macroinitiator and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomer. The structure of the prepared hyperbranched star polymer was characterized by ¹H NMR, ATR-FTIR, and GPC. Polymer electrolytes based on HBPS-(PPEGMA) _x , lithium salt, and/or nano-TiO₂ were prepared. The influences of lithium salt concentration and type, nano-TiO₂ content, and size on ionic conductivity of the obtained polymer electrolytes were investigated. The results showed that the low crystallinity of the prepared polymer electrolyte was caused by the interaction between lithium salt and polymer. The addition of TiO₂ into HBPS-(PPEGMA) _x /LiTFSI improved the ionic conductivity at low temperature. The prepared composite polymer electrolyte showed the highest ionic conductivity of 9?×?10^?5 S cm^?1 at 30 °C when the content of TiO₂ was 15 wt% and the size of TiO₂ was 20 nm.     

Löslichkeit,Diffusion und Ultrarotabsorption von Wassermolekülen in Alkalihalogenidkristallen

Following a former communication, further experiments of solubility, diffusion and infraredabsorption of water molecules in KCl-, KBr- and KJ-crystals are given. Substituted mono- and bivalent ions to the refined crystals strongly increase the solubility of water at lower temperatures but there is practically no increase at higher temperatures. This points to two mechanisms for solubility: An interstitial at lower temperatures and probably by vacancies at higher temperatures. — The penetration of water into crystals containing K₂O orF-centers produces a colorless layer by chemical reaction. From investigation of such layers we get diffusion constants for the diffusion of water molecules. In crystals containingF-centers we find an additionalKH- layer. — The chemical reactions in the solid state produce H^?-, OH^?- and O^??-centers of well known concentration. This allows determination of the oscillator strengths of the characteristical ultraviolett absorptions. — The absorption in the near infrared by crystals containing water shows especially at low temperatures sharp peaks from single H₂O-molecules and broad peaks from precipitated water. An interstitial lattice model is discussed for the single H₂O-molecules.     

Magnetic structure and transport properties of atomically disordered crystals of two-dimensional manganites La2−2x Sr1+2x Mn2O7

The magnetic structure and transport properties of partially disordered crystals of two-dimensional manganites La_2?2x Sr_1+2x Mn₂O₇ (x = 0.3, 0.4) are studied over a wide range of temperatures. The crystals are transformed into an atomically disordered state under irradiation with fast neutrons at a dose of 2 × 10¹⁹ cm^?2. The average concentration of substitutional defects in the crystal is ≈4%. It is found that substitutional defects are responsible for the transition of these manganites from the ferromagnetic metal state to the insulator state with a spin glass structure. The results obtained are discussed in terms of the ratio between the kinetic energy of charge carriers and the exchange energy of localized spins.