Permeation through latent nuclear tracks in polymer foils

The stable defects created in most dielectrica by fast heavy ions, called latent nuclear tracks, are zones of reduced density. Using the small-angle neutron-scattering technique it is shown that water molecules which permeate a polymer foil are preferentially embedded in these zones. In the track region the diffusion- and the sorption coefficients for various atoms and molecules are larger than in unirradiated material. In the damaged region of tracks produced by uranium ions in Polyethyleneterephtalate (PETP) the permeability for neon, oxygen, argon, carbondioxide, and water is enhanced by factors between 60 and 290.A method for the preferential etching of latent nuclear tracks in PETP using methanol as a solvent is suggested.Part of the dissertation, Univ. Giessen (D26), Fed. Rep. Germany     

Modification of Ti foils irradiated by intense heavy ion beams

ABSTRACT

Modification of Ti foils irradiated by intense energetic heavy ion (HI) beams in long-term experiments has been considered. The experiments on the synthesis of superheavy nuclei, which are carried out in Dubna with a gas-filled recoil separator (DGFRS), determine the conditions of such experiments. High intensities of HIs passing through a relatively small area and thickness of the foils, as well as their heating by a beam, are inherent in such experiments. The ability of the foils to withstand radiation damages, sputtering, and evaporation of atoms becomes questionable. All the processes seem to be dependent on temperature, and none of them is independent of the others, but they can be considered separately. In this work, sputtering yields are estimated on the grounds of available models and experimental data and compared with the results of measurements carried out to verify the estimates. The foil temperature, in turn, can be estimated in the conditions of pulse heating followed by subsequent cooling with radiation emitted from their surfaces. These conditions correspond to the rotating Ti entrance window irradiated by a continuous HI beam in the DGFRS experiments.     

Evidence of ion pair breaking by dispersed polymer in polymer gel electrolytes

Non-aqueous polymer gel electrolytes containing trifluoromethanesulfonic acid (HCF₃SO₃) and polyethylene oxide (PEO) as the gelling polymer has been studied. The increase in conductivity observed with the addition of PEO to liquid electrolytes has been explained to be due to the breaking of ion aggregates present in electrolytes at higher acid concentrations. The increase in free H⁺ ion concentration upon breaking of ion aggregates has also been observed in pH measurements and viscosity of gel electrolytes has been found to increase with PEO addition. Polymer gel electrolytes containing dimethylacetamide (DMA) have σ ∼ 10⁻² S/cm at room temperature and are stable over −50 to 125 °C range of temperature. Gels based on propylene carbonate (PC) and ethylene carbonate (EC) are stable in the −50 to 40 °C temperature range and loose their gelling nature above 40 °C.     

Evidence of ion pair breaking by dispersed polymer in polymer gel electrolytes

Non-aqueous polymer gel electrolytes containing trifluoromethanesulfonic acid (HCF₃SO₃) and polyethylene oxide (PEO) as the gelling polymer has been studied. The increase in conductivity observed with the addition of PEO to liquid electrolytes has been explained to be due to the breaking of ion aggregates present in electrolytes at higher acid concentrations. The increase in free H⁺ ion concentration upon breaking of ion aggregates has also been observed in pH measurements and viscosity of gel electrolytes has been found to increase with PEO addition. Polymer gel electrolytes containing dimethylacetamide (DMA) have σ ∼ 10⁻² S/cm at room temperature and are stable over −50 to 125 °C range of temperature. Gels based on propylene carbonate (PC) and ethylene carbonate (EC) are stable in the −50 to 40 °C temperature range and loose their gelling nature above 40 °C.     

Li ion conduction on plasticizer-added PVAc-based hybrid polymer electrolytes

Poly(vinyl acetate), poly(vinylidene fluoride–hexafluoropropylene), lithium perchlorate salt, and the different plasticizer-based gel polymer electrolytes were prepared by solvent-casting technique. The structural and the complex formation have been confirmed by X-ray diffraction spectroscopic analysis. Thermal stability of the different plasticizer-added electrolyte films has been analyzed by means of thermogravimetric analysis. Ionic conductivity of the electrolyte samples has been found as a function of temperature and the plasticizers. Among the various plasticizers, ethylene carbonate-based complexes exhibit maximum ionic conductivity value of the order of 10⁻⁴ Scm⁻¹. Finally, the microstructure of the maximum ionic conductivity sample has been depicted with the help of scanning electron microscope analysis.     

Growth of iron single crystals in the etched ion tracks of polymer foils

Pulse reverse electrolysis in an ultrasonic field is used to grow iron single crystals of micron size in templates formed by etching the tracks of swift ions in polymer foils. High-grade crystals are produced from high-temperature ferrous chloride baths. The crystals are oriented along their <110>, <100>, and <111> crystallographic axes. Their orientation turns out to depend on supersaturation during the growing process. At low overvoltages of deposition, <110> and <100> orientations are observed. The crystals of <111> orientation appear more frequently at higher cathode pulse current density. The crystals possess prominent resistance to corrosion. Received: 20 February 2001 / Accepted: 21 February 2001 / Published online: 3 May 2001     

Blended lithium ion conducting polymer electrolytes based on boroxine polymers

A new series of blended polymer electrolytes based on a boroxine polymer (BP) with poly(ethylene oxide) (PEO), an ethylene oxide–propylene oxide copolymer or poly(methyl methacrylate) were prepared. Good room temperature mechanical properties were exhibited by electrolytes containing in excess of 30% PEO. Cationic transference number measurements indicated that a slight improvement in lithium ion conductivity could be achieved by using a mixture of LiCF₃SO₃ and LiN(CF₃SO₂)₂ as the electrolyte salt. Electrolytes incorporating significant proportions of BP exhibited reduced lithium–polymer electrolyte interfacial resistance.     

Observation of diffusion through ion irradiated Makrofol KG

The features of the latent track in polycarbonate can be analysed by measuring the diffusion constant under ultra high vacuum conditions. Stacks of 30 μm Makrofol KG foils were irradiated with uranium ions of 11.4 MeV/u at the GSI Darmstadt, Germany. We used different fluences from 3·10¹⁰ to 5·10¹¹ ions/cm². The diffusion constant was determined by the time-lag-method [1]. A quadrupole mass filter was used to observe the diffusion of the gas. We measured the diffusion of argon through different foils of each stack at room temperature. In all cases also unirradiated foils were measured. The dependence of the permeability and the diffusion constant on the ion fluence and the energy loss of the ions will be given and indications on the size of latent ion tracks concerning gas diffusion will be discussed.     

A quantum-chemical study on ion complexation in polymer electrolytes containing lithium aluminate salts

A quantum-chemical study on single-ion conducting electrolytes based on lithium aluminate salts is presented. Geometry optimizations for salts and corresponding anions have been performed. Stabilization energies for Li⁺ complexed at aluminate anions have been calculated. Information about Li⁺ coordination changes has been obtained from Born–Oppenheimer Molecular Dynamics simulations. Complexation energies for lithium cation have been shown to correlate with experimental conductivity values [T. Fujinami, Y. Buzoujima, J. Power Sources 119–121 (2003) 438].     

Spectroscopic studies of triflate ion association in polymer gel electrolytes and their constituents

Raman and NMR spectroscopy have been used to investigate the state of ion association in systems comprising salt, polymer and/or solvent. The dissolved salt in each case was lithium triflate (lithium trifluoromethane sulphonate). Five systems were studied, comprising polymer gel electrolytes or constituents of such electrolytes. These were: salted (a) N,N'-dimethyl formamide (DMF), (b) tetraethylene glycol dimethylether (tetraglyme), (c) polyethylene glycol (PEG), (d) end-esterified PEG and (e) poly(vinylidene fluoride) (PVDF) gels containing either DMF or tetraglyme. Raman results give a broad indication of the significance of end-group, solvent and polymer choice in triflate-salted systems. In all cases, anion association rises with temperature, often with a significant increase in ion aggregation. The reliability of these results is supported by an analysis of systematic errors incident in this technique for ion association measurements. A limited comparison performed on the system having the highest concentration of ion aggregates (end-esterified PEG) suggests that Raman and NMR spectroscopy provide different information concerning ion association. Reasons for the difference are discussed, concluding that complementary information is obtained owing to the different time constants relevant to the two techniques and to the dependence of the Raman results on molecular proximity.     

Durability of targets and foils irradiated by intense heavy ion beams in experiments on synthesis of superheavy nuclei

Durability of targets and window foils irradiated by intense heavy ion (HI) beams in the experiments on synthesis of superheavy nuclei, which are carried out in Dubna with Gas-Filled Recoil Separator (DGFRS), has been viewed in various ways. High fluxes of HI and heat generations, which are realized within relatively small areas and thicknesses of these elements of DGFRS, are inherent in such experiments. The lifetimes of the targets and window foils are estimated as the result of HI beam actions such as radiation damages, sputtering and evaporation of atoms. The most critical processes determining the durability of the targets and window foils are discussed. The processes of heat transfer due to thermal conductivity, convection and radiation are also considered from the point of view of possible ways of cooling of the elements irradiated by an intense HI beam. Temperatures of the targets and window foils as functions of time are calculated in the conditions of their pulse heating by the beam followed by radiative cooling of their surfaces. Such pulsing mode is realized in the DGFRS operation with the rotation of target and window foils irradiated by a continuous HI beam. Estimates show that radiative cooling in such conditions can be the most effective way of heat removal at the temperature of several hundred degrees. Such temperature can be reached on the surfaces of the target and window foils irradiated by HI beams at the intensity ~10¹³ s^–1.     

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.     

Investigations on Na+ ion conducting polyvinylidenefluoride-co-hexafluoropropylene/poly ethylmethacrylate blend polymer electrolytes

Sodium ion conducting composite polymer electrolytes (CPE) have been prepared by solution casting technique in the skeleton of polyvinylidenefluoride-co-hexafluoropropylene/poly ethylmethacrylate blend. The binary mixture of diethyl carbonate and ethylene carbonate were used as plasticizer, and nanosized Sb₂O₃ as filler. The sodium trifluoromethanesulfonate (NaCF₃SO₃) was used as an ionic conducting source. The a.c. impedance study shows that 10 wt% Sb₂O₃ containing CPE exhibits the maximum conductivity 0.569 mS cm⁻¹ at ambient temperature. Molecular interactions of the constituents were analyzed by Fourier transform infra red spectroscopy. X-ray diffractogram reveals the amorphous nature of the CPE. A surface morphological feature was studied through scanning electron microscope. The activation energy and coherence length calculated were in support of the ionic transport.     

Dielectric relaxation in PEO-based polymer electrolytes

Dielectric properties of cross-linked poly(ethylene oxide) (PEO) with different mesh sizes, doped with lithium salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), have been studied in frequency region between 0.1 and 10⁷ Hz and in broad temperature range. Results were compared with linear PEO of 1000 g/mol. Dielectric responses of the systems are dependent on frequency and thermally activated. Systems exhibit different responses in semi-crystalline and molten state. Increase of temperature promotes polarization; whereas, increase of frequency lessens it. In other words, polarization is thermally activated and local conductivity reduced. Generally, one observes enhanced dc conductivity in linear PEO as compared to cross-linked PEO at high temperature and the opposite at low temperature. Resonance responses are observed in low-molecular cross-linked PEO and in linear PEO at low temperature. These responses lead to splitting of polarization relaxation at frequencies beyond low-frequency range. Salt-comprising systems display only relaxation-type dielectric response. Imaginary parts of response spectra show distribution of relaxation times. It turns out that this distribution is independent of temperature in the low-frequency range, but depends on concentration of salt in the cross-linked polymer. In both systems, neat cross-linked and linear polymer of low-molecular mass, one observes coexistence of non-local and local motions of charged entities even at very low temperature.     

Ionic noise measurement in polymer electrolytes

Electrical noise associated with ion transport (termed as “ionic noise”) has been measured at different temperatures, using a lock-in amplifier and dynamic signal analyzer for a polymer electrolyte PEO:NH₄I and its CdS dispersed composite. The ionic noise suddenly increases as the polymer passes through its phase transition at T _g and T _m. The T _g-peak in the noise measurement appears more clearly than what it does in DTA/DSC or conductivity measurements. Therefore, we suggest the noise technique as a good probe for studying phase transitions in ion conducting solid electrolytes. Further, the present noise measurements also confirm the known results of DTA/DSC studies that both T _g and T _m of polymer electrolytes shift on the formation of composites.     

Dielectric spectroscopy and confirmation of ion conduction mechanism in direct melt compounded hot-press polymer nanocomposite electrolytes

Solid-type polymer nanocomposite electrolyte (PNCE) comprising poly(ethylene oxide) (PEO), lithium perchlorate (LiClO₄) and montmorillonite (MMT) nano-platelets were synthesized by direct melt compounded hot-press technique at 70 °C under 3 tons of pressure. The spectra of complex dielectric function, electric modulus and alternating current (ac) electrical conductivity, and complex impedance plane plots of these materials were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The variation of electrode polarization and ionic conduction relaxation times with MMT concentration up to 20 wt.% confirms their strong correlation with direct current ionic conductivity. The predominance of exfoliated MMT structures in PEO matrix and their effect on cation conduction mechanism and ion pairing were discussed by considering a supramolecular transient cross-linked structure. The normalized ac conductivity as a function of scaled frequency of these PNCE materials obey the universal time–concentration superposition behaviour alike the disordered solid ionic conductors.     

Electrical properties of plasticized chitosan-lithium imide with oleic acid-based polymer electrolytes for lithium rechargeable batteries

Solid polymer electrolytes (SPEs) were prepared and their electrochemical characteristics were characterized. The composition of SPEs containing chitosan, lithium trifluoromethane sulfonimide (LiN(CF₃SO₂)₂) and oleic acid (OA) was optimized employing ac impedance measurements at various temperatures. The electrical conductivity of the SPEs with OA shows the highest value and the presence of OA does not change the structure of the polymer. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.