Poly(ethylene oxide-co-epichlorohydrin)/NaI: a promising polymer electrolyte for photoelectrochemical cells

We have investigated the thermal and ionic conductivity properties of the elastomer poly(ethylene oxide-co-epichlorohydrin) filled with NaI and I₂. The reason for using this composition is its potential application as electrolyte in photoelectrochemical cells. This copolymer was characterized as a function of NaI concentration, temperature and relative humidity. According to the data obtained, the Na⁺ ion interacts with the ethylene oxide repeating units by means of Lewis type acid–base interactions. The empirical Vogel–Tamman–Fulcher equation was used to model the conductivity and temperature relationships, indicating that the conduction occurs in the amorphous phase of the copolymer. The sample with 9.0% (w/w) of NaI presents a conductivity of 1.5×10⁻⁵ S cm⁻¹ in a dry atmosphere (30°C, [H₂O]<1 ppm) and 2.0×10⁻⁴ S cm⁻¹ at 86% relative humidity (22°C).     

High temperature transport processes in lithium niobate

The electrical conductivity of single crystal lithium niobate (LiNbO₃) was determined as a function of temperature for various oxygen partial pressures. The electrical conductivity is proportional to P_o2^−1/4 which can be explained by a defect equilibrium involving singly ionized oxygen vacancies and electrons.

Measurements of electrical transport numbers at 1000°K show the electrical conductivity of LiNbO₃ to be ionic at one atmosphere of oxygen and electronic at low oxygen partial pressures.

Thermoelectric measurements indicate that LiNbO₃ at low oxygen partial pressures is n-type and that the concentration of electrons at 1000°K and in an atmosphere of 50% C0/50% CO₂a is 4 × 10¹⁷cm³ with a mobility of 1.7 cm²V sec.

The diffusion of oxygen in LiNbO₃ was determined as a function of temperature at an oxygen partial pressure of 70 Torr. by measuring O¹⁸/O¹⁶ isotope exchange with the gas phase as a function of time. The diffusion data may be represented by D = 3.03 × 10⁻⁶ exp (−29.4 kcal mole⁻¹/RT)cm²sec. Consideration of the Nernst-Einstein relation for oxygen and the variation in conductivity with Li₂O activity indicate that the ionic conduction is caused by transport of lithium ions.     

Proton conductive amorphous thin films of tungsten oxide clusters with acidic ligands

Three kinds of peroxo-polytungstic acid (PPTA, C-PPTA and N-PPTA) were obtained by reacting hydrogen peroxide with metallic tungsten, tungsten carbide or tungsten nitride, respectively. Polytungstates, C-PPTA and N-PPTA, were found to contain oxalate and nitrate ligands. Their proton conductivities were compared using thin film specimens spin-coated from their water solution. Conductivity of each as-coated film was in the range from 10⁻³ to 10⁻⁴ S cm⁻¹ under the relative humidity of 40% (25 °C). A sharp decrease in conductivity (to less than 10⁻⁷ S cm⁻¹ at 25 °C) was observed for PPTA without acidic ligands after thermal treatment at 80 °C. However, the effect of thermal treatment on C-PPTA or N-PPTA was much milder. A 80 °C-treated C-PPTA film showed the conductivity of 1.0 × 10⁻⁵ S cm⁻¹ (25 °C) with a very weak dependency on ambient humidity.     

Proton conductivity of phosphoric acid derivative of fullerene

The proton conductive property of methano [60] fullerene diphosphoric acid has been investigated under various humidity conditions at the temperature range between 15 and 45 °C. It shows proton conductivity as high as 10⁻² S cm⁻¹ at 25 °C under relative humidity of 95%. Thermal analyses including TG–DTA and thermal desorption mass spectroscopy (TDS) confirm that the compound is thermally stable up to 200 °C. Proton conduction of the compound depends very much on humidity or water content. The logarithmic conductivity at 25 °C is increased linearly with increasing relative humidity. The activation energy (E_a) estimated from the slope of log(σT) vs. 1/T is decreased from 1.08 to 0.52 eV, as the relative humidity is increased from 40% to 75%. The humidity dependence of conductivity is discussed in the light of the observed hydration isotherm.     

Conductivity anisotropy in directionally solidified CaZrO3---CaSZ and MgO-MgSZ eutectics

The results of the impedance spectroscopy measurements on eutectic samples based on zirconium oxide are presented here. Samples of CaZrO₃---ZrO₂(cubic) and MgO---ZrO₂(cubic) have been grown by a directional solidification procedure such that the different phases appear nearly oriented along the growth direction (lamellae in the system of CaZrO₃-ZrO₂(cubic) and fibers of MgO in a ZrO₂ matrix in the other system). The DC electrical conductivity has been measured by impedance spectroscopy along and across the growth axis. For CaZrO₃---ZrO₂ the coductivity is clearly anisotropic. The following values for σT have been obtained: the conductivity at 600 °C equals 2.0 × 10⁻⁶ Ω⁻¹ cm⁻¹ perpendicular to the fiber axis and 1.4 × 10⁻⁵ Ω⁻¹ cm⁻¹ parallel to it and with an activation energy of 1.3 eV for σT. For MgO---ZrO₂(cubic) the isotropic value of the conductivity at 600 °C is 10⁻⁴ Ω⁻¹ cm⁻¹ with activation energy for σT of 1.5 eV. The anisotropic conductivity in the CaZrO₃---ZrO₂ (cubic) system has been explained by a model of an ordered stacking of oxygen conducting (cubic ZrO₂) and non-conducting (CaZrO₃ or MgO) phases.     

Chemically deposited copper oxide thin films: structural, optical and electrical characteristics

Thin films of copper oxide with thickness ranging from 0.05–0.45 μm were deposited on microscope glass slides by successively dipping them for 20 s each in a solution of 1 M NaOH and then in a solution of copper complex. Temperature of the NaOH solution was varied from 50–90°C, while that of the copper solution was maintained at room temperature. X-ray diffraction patterns showed that the films, as prepared, are of cuprite structure with composition Cu₂O. Annealing the films in air at 350°C converts these films to CuO. This conversion is accompanied by a shift in the optical band gap from 2.1 eV (direct) to 1.75 eV (direct). The films show p-type conductivity, 5×10⁻⁴ Ω⁻¹ cm⁻¹ for a film of thickness 0.15 μm. Electrical conductivity of this film increases by a factor of 3 when illuminated with 1 kW m⁻² tungsten halogen radiation. Annealing in a nitrogen atmosphere at temperatures up to 400°C does not change the composition of the films. However, the conductivity in the dark as well as the photoconductivity of the film increases by an order of magnitude. The electrical conductivity of the CuO thin films produced by air annealing at 400°C, is high, 7×10⁻³ Ω⁻¹ cm⁻¹. These films are also photoconductive.     

Determination of different oxygen transport mechanisms and measurement of the oxygen ion conductivity of Y1Ba2Cu3O7−x

By undertaking AC electrochemical impedance experiments on yttria stabilised zirconia electrolytes with polished Y₁Ba₂Cu₃O_7−x electrodes, the activation energy for oxygen ion transport within the bulk of Y₁Ba₂Cu₃O_7−x, in air, over the temperature range 823 K–1043 K, was determined to be 1.50 ± 0.05 eV. At 1000 K the oxygen ionic conductivity was calculated to be around one order of magnitude lower than that in yttria stabilised zirconia. Typical calculated values were σ=5×10⁻⁵ (ω cm)⁻¹ and 6×10⁻³ (ω cm)⁻¹ at the respective temperatures 823 K and 1043 K. By employing a similar cell but with Y₁Ba₂Cu₃O_7−x paste electrodes, oxygen transfer between the Y₁Ba₂Cu₃O_7−x and the electrolyte was found to occur via a surface diffusional processes. Over the temperature range 873 K–1098 K, in air, the activation energy for in-diffusion at the surface was found to be 1.4±0.1 eV and that for out-diffusion at the surface to be 1.76±0.05 eV.     

Polymer electrolytes based on ethylene oxide–epichlorohydrin copolymers

In this work we studied the ionic conductivity for three copolymers of the title co-monomers as a function of LiClO₄ content, temperature and ambient relative humidity. We also investigated the interactions between the salt and the co-monomer blocks in the copolymers and its effect on the morphology and thermal properties of the copolymer/salt complexes. Our data indicate that the Li⁺ ion predominantly interacts with the ethylene oxide repeating units of the copolymers. The copolymer with the highest ionic conductivity was obtained with an ethylene oxide/epichlorohydrin ratio of 84/16 containing 5.5% (w/w) of LiClO₄. It showed a conductivity of 4.1×10⁻⁵ S cm⁻¹ (30°C, humidity< 1 ppm) and 2.6×10⁻⁴ S cm⁻¹ at 84% relative humidity (24°C). The potential stability window of the copolymer/salt complex is 4.0 V, as measured by cyclic voltammetry. For comparison, we also prepared a blend of the corresponding homopolymers containing LiClO₄; it showed higher crystallinity and lower ionic conductivity.     

Ionic conduction and dielectric relaxation in Ag/Na ion-exchanged aluminosilicate glasses: mixed mobile ion effect and KWW relaxation

Ag⁺/Na⁺ ion-exchanged aluminosilicate glasses with uniform concentration profiles were prepared, and their electrical conductivities were investigated as functions of the ion-exchange ratio and the initial glass compositions. In the case of the ion-exchanged glasses of x20Ag₂O–(1−x)20Na₂O–10Al₂O₃–70SiO₂ in mol%, the conductivity, σ, and its activation energy, E_σ, showed a minimum and a maximum at the same ion-exchange ratio x=0.3, respectively, and the mixed mobile ion effect (MMIE) was observed. The fully ion-exchanged sample attained σ=3.5×10⁻⁵ S/cm at 200 °C, which was 1.5 orders of magnitude larger than that of initial glass. In the case of x25Ag₂O–(1−x)25Na₂O–25Al₂O₃–50SiO₂, the mixed mobile ion effect was also observed at x=0.5. The maximum conductivity of 2×10⁻⁴ S/cm at 200 °C was obtained in the fully ion-exchanged glass sample.

The electric relaxation analysis was also conducted on both systems, and Kohlrausch–Williams–Watts (KWW) fractional exponent β was obtained as a function of x. The decrease of β was observed near x≈0.3 in the former system, while that of the later system was independent of the ion-exchange ratio. Based on the structural analysis results, the observed behaviors were investigated from the point of view of the occupation of Ag⁺ ions on the non-bridging oxygen-site (NBO-site) and the charge compensation-site (CC-site) of AlO₄ tetrahedral unit.     

A new measurement of the weak magnetism term in the betaspectra of B and N

The betaspectra of ¹²B and ¹²N have been measured with a NaI crystal as spectrometer. Assuming a shape correction factor 1 + aW + bW² and b₋ = 1.106 × 10⁻⁴ MeV⁻², b₊ = −1.397 × 10⁻⁴ MeV⁻², the spectra yield a₋ = (+0.91 ± 0.11) × 10⁻² MeV⁻¹ and a₊ = (−0.07 ± 0.09) × 10⁻² MeV⁻. the a₋ − a₊ = (+0.98 ± 0.09) × 10⁻² MeV⁻¹ is in agreement with the weak magnetism prediction.     

Diffusion of W on A W(211) plane

The diffusion of W on a (211) plane of a W field emitter has been re-examined by means of the fluctuation autocorrelation method. Diffusion along channels yielded E = 16.8 ± 0.5 kcal, D₀ = (3 ± 1) × 10⁻⁵ cm² s⁻¹. For diffusion across channels E =6.6 kcal, D₀ = 4 × 10⁻⁹cm² s⁻¹ at T < 752 K, and E = 24 kcal, D₀ = 5 × 10⁻⁴ cm² s⁻¹ at T > 752 K. The results for diffusion along channels yield E and D₀ values intermediate between recent results by Wang and Ehrlich [Surf. Sci. 206 (1988) 451] using field ion microscopy (E = 19 kcal, D₀ = 7.7 × 10⁻³ cm² s⁻¹) and Tringides and Gomer [J. Chem. Phys. 84 (1986) 4049], using the same method as the present work but a larger slit (E = 13.3 kcal, D₀ = 7 × 10⁻⁷ cm² s⁻¹). The results for cross channel diffus good agreement with those of Tringides and Gomer below 752 K, where these authors stopped. The new high temperature results suggest that the channel wall exchange mechanism postulated by Tringides and Gomer for cross channel diffusion at low T gives way to diffusion by climbing over the channel walls with higher E but also higher D₀ above 752 K. Possible reasons for the discrepancies between these three sets of results and the absence of cross channel diffusion in the work of Wang and Ehrlich are briefly discussed.     

Absolute desorption yields of metastable atoms from the surface of solid rare gases induced by exciton creation

Absolute yields of the metastable excited atoms desorbed from the surfaces of solid Ne and Ar by the creation of surface and bulk excitons have been measured using monochromated synchrotron radiation as a selective excitation source. We have obtained the absolute yields of (2.3 ± 0.7) × 10⁻³, (1.4 ± 0.4) × 10⁻³, and (7.8 ± 2.3) × 10⁻⁴ atoms/photon at the excitation of S1, B1 and S′ exciton for Ne, respectively, and 1 × 10⁻⁵ atoms/photon at S1 excitation for Ar. The probability for metastable atom desorption is found to be about 2 to 10% at the excitation of S1 exciton on the surface of solid Ne.     

Preparation and characterization of a lithium ion conducting electrolyte based on poly(trimethylene carbonate)

In this paper, the results of preliminary studies of two new solvent-free polymer electrolytes based on poly(trimethylene carbonate), p(TMC), with lithium trifluoromethanesulphonate, (triflate), and lithium perchlorate are described. Thin films of these electrolytes were obtained by evaporation of solvent from homogeneous mixtures of known masses of host polymer and salt. Electrolytes with compositions of n between 1.5 and 85, where n represents the molar ratio of (O=COCH₂CH₂CH₂O) units per lithium ion, have been prepared. These solvent-free electrolytes were characterized by measurements of total ionic conductivity, differential scanning calorimetry (DSC) and thermogravimetry (TGA). As expected from previous studies with these salts in poly(ethylene oxide), PEO, the triflate-based system showed superior thermal stability but with a lower total ionic conductivity than that of the perchlorate-containing electrolyte. The highest conductivity (approximately 3×10⁻⁴ Ω⁻¹ cm⁻¹) was found at 95°C with the electrolyte composition of (TMC)₂LiClO₄.     

Observation of two-photon emission in nuclear pion capture

The emission of two photons above 25 MeV energy was observed in the capture of stopped pions by beryllium and carbon with a rate of (1.0 ± 0.1) × 10⁻⁵, respectively (1.4 ± 0.2) × 10⁻⁵ per capture. These rates are about two to four times greater than various free-nucleon estimates based on the π⁻+π⁺→γγ annihilation mechanism alone.     

Optical pumping of the 2p3sP0 State of Ne (I = 3/2): g factor and metastability exchange cross section

A C.W. multi-mode dye laser is used to obtain by optical pumping an orientation of the 2p⁵ 3s³P₀ (F = 3/2) state of ²¹Ne. A magnetic resonance experiment leads to the measurement of the g factor g (³P₀) = 3.027 (8) × 10⁻⁴ to be compared with the theoretical prediction (3.025(6) × 10⁻⁴). One obtains also the metastability exchange cross section σ(³P₀) = 18.4 ± 4 Ų for collisions between metastable (³P₀) Ne atoms and ground state Ne atoms. This result is compared with other measurements and theoretical evaluation.     

Davydov splitting and two-photon excitation of cadmium tungstate (CdWO4) single crystal phosphorescence

Phosphorescence characteristics of CdWO₄ excited by one-photon (λ = 308 nm) and two-photon (λ = 570–590 nm) processes were measured. A Davydov splitting of 120 ± 20 cm⁻¹ was obtained in the phosphorescence spectra, suggesting a diffusion coefficient of about 1.2 × 10⁻² cm² s⁻¹, and a diffusion length of about 3.1 × 10⁻⁴ cm for the room temperature measured lifetime of 8μs. The phosphorescence quantum efficiency was less than 2% at low temperatures (only 0.25% at room temperature), indicating that the dominant decay mechanism was radiationless. The radiative lifetime was thus estimated as 1–2 ms. The two-photon phosphorescence excitation is characterized by an absorption cross-section of the order of 10⁻⁴⁹cm⁴s.     

Study of cluster decay of Cm using SSNTD

Cluster decay of ²⁴²Cm with emission of ³⁴Si-particles was measured using track-recording phosphate glass detectors. The corresponding partial half-life is (1.4±0.3)×10²³ s. The branching ratio relative to decay is 1.0×10⁻¹⁶ and relative to spontaneous fission 1.6×10⁻⁹.     

Optical nonlinearities and photo-excited carrier lifetime in CdS at 532 nm

Bound-electronic and free-carrier optical nonlinearities, and relaxation of photo-excited free carriers in CdS have been investigated by the use of a single-beam Z-scan technique at 532 nm. Under pulsed radiation of 35-ps duration with the input irradiances up to 4.8 GW/cm², the two-photon absorption coefficient, the bound-electron nonlinear refractive index, the free-carrier absorption cross-section, and the change in the refractive index per unit carrier density are determined to be 5.4±0.8 cm/GW, −(5.3±0.8)×10⁻¹³ cm²/W, (3.0±0.5)×10⁻¹⁷ cm² and −(0.8±0.1)×10⁻²¹ cm³, respectively. By using these values in the open-aperture Z-scans conducted with 7-ns laser pulses, the carrier recombination time is extracted to be 3.6±0.7 ns. The measured parameters are compared to theoretical calculations.     

Measurement of diffusion coefficients using a quick echo split NMR imaging technique

A new method for the ultrafast generation of diffusion-weighted images is reported. The technique combines a quick echo split NMR imaging sequence with the principle of Stejskal and Tanner. It allows to determine the diffusion constant with nearly the same accuracy as the conventional spin-echo technique, requiring only a fraction of the time. The determined values for water doped with 1 g Cu(NO₃)₂ per liter of H₂O and pure acetone were D_water = (1.95 ± 0.02) × 10⁻⁹ m²/s and D_acetone = (4.05 ± 0.02) × 10⁻⁹ m²/s at 18.5°C. They are in good agreement both with literature and our own reference measurements using a diffusion-weighted spin-echo sequence. In addition, the temperature dependence of D_water was measured in the range of 18.5–45.9°C and a good correspondence with reported data was found.     

Preliminary results on Cu diffusion through grain boundaries of thin ion-plated Ag---Sn films

The diffusion process of copper through grain boundaries of 500 nm thick ion-plated Ag-12at%Sn films was studied in the temperature range 100–250°C. The method is based on the determination of the time of first appearance of Cu on the Ag---Sn surface using Auger electron spectroscopy for determining trace amounts of Cu. An activation energy of E_a = 0.53 eV and a diffusivity of D′_o = 1.3 × 10⁻⁷cm²s⁻¹ was obtained. For comparison, diffusion studies of Cu through ion-plated pure Ag layers have been performed. In this case an activation energy of E_a = 0.68 eV and a diffusivity of D′_o = 2.3 × 10⁻⁵cm²s⁻¹ have been found.