Coupled chemical reactions in dynamic nanometric confinement: V. The influence of Li+ and F− ions on etching of nuclear tracks in polymers

Etching of continuous nuclear tracks in thin polymer foils from both sides is known to lead to the formation of double-conical nanopores. In this work and related ones we try to find out how this etching kinetics is modified when materials are added which react with each other upon their contact towards some new product that influences the etching. For that purpose we have chosen here Li⁺ and F^? ions as the additions, which react with each other to form LiF precipitations. The coupled etching and precipitation kinetics is recorded by measuring the electrical current that is transmitted through the foils upon application of a low-frequency alternating sinusoidal voltage. Depending on the etchant concentrations, the etching temperature and the time of Li⁺ and F^? addition, different effects are found that range from (a) no alteration of the transmitted current at all, via (b) the emergence of an alternating current with a temperature-dependent amplitude, and (c) the complete vanishing of any transmitted current at all, towards (d) chaotic transmitted current histories with phases with strong current spike emission and (e) rather quiet phases, alternating with each other in a rather unsystematic way. The observed effects are ascribed to (a) the enhanced penetration efficiency of both the Li⁺ and F^? ions through the polymeric bulk and/or latent ion tracks after the removal of the polymer's protective surface layer by the etchant, (b) the high mobility of preferentially the F^? ions within the polymer, (c) the LiF precipitation within the polymer or on its surface upon encounter of Li⁺ and F^? ions, (d) the nanofluidic properties of narrow etched tracks covered with Li⁺ ions on the wall surfaces and F^? ions beyond, and/or (e) the formation of LiF membranes within the etched tracks.     

Coupled chemical reactions in dynamic nanometric confinement: Ag2O membrane formation during ion track etching

In this study, continuous swift heavy ion tracks in thin polymer foils were etched from both sides to create two conical nanopores opposing each other. Shortly before both cones merged, one of the nanopores was filled with a silver salt solution, whereas etching of the other cone continued. At the moment of track breakthrough, the etchant reacted with the silver salt solution by forming an impermeable and insulating membrane. Continued etching around the thus-created obstacle led to repetitive {etchant – silver salt solution} interactions. The coupling of the two chemical reactions, {etchant – polymer} and {etchant – silver salt solution}, within the confinement of etched tracks, with continuously changing shapes, showed a highly dynamic nature as recorded by measuring both the electrical current and the optical transmission across the foils. At low etching speeds, a central membrane that grew in radius and thickness with time until, at a critical thickness, the membrane became rather impermeable was formed. However, at high etching speeds, the emerging reaction products exhibited a sponge-like consistency, which allowed for their infinite growth. This precipitation was accompanied by a pronounced current spike formation. A simple theoretical model explains, at a minimum, the basic features.     

SHI induced nano track polymer filters and characterization

Swift heavy ion irradiation produces damage in polymers in the form of latent tracks. Latent tracks can be enlarged by etching it in a suitable etchant and thus nuclear track etch membrane can be formed for gas permeation / purification in particular for hydrogen where the molecular size is very small. By applying suitable and controlled etching conditions well defined tracks can be formed for specific applications of the membranes. After etching gas permeation method is used for characterizing the tracks. In the present work polycarbonate (PC) of various thickness were irradiated with energetic ion beam at Inter University Accelerator Centre (IUAC), New Delhi. Nuclear tracks were modified by etching the PC in 6N NaOH at 60 (±1) °C from both sides for different times to produce track etch membranes. At critical etch time the etched pits from both the sides meet a rapid increase in gas permeation was observed. Permeability of hydrogen and carbon dioxide has been measured in samples etched for different times. The latent tracks produced by SHI irradiation in the track etch membranes show enhancement of free volume of the polymer. Nano filters are separation devices for the mixture of gases, different ions in the solution and isotopes and isobars separations. The polymer thin films with controlled porosity finding it self as best choice. However, the permeability and selectivity of these polymer based membrane filters are very important at the nano scale separation. The Swift Heavy Ion (SHI) induced nuclear track etched polymeric films with controlled etching have been attempted and characterized as nano scale filters.      

Electrical characteristics of etched ion-tracks in polyimide filled with silver nanoparticles

Silicon ions, of energy 150?MeV and fluence ～10¹²?ions/cm², were used to register latent tracks in 40?µm thick polyimide samples. Different sizes of tracks were obtained by etching the ion irradiated polyimide samples, in chemical solutions, by varying the temperature and etching period. Silver nanoparticles were diffused into the etched tracks by immersing the polyimide samples in silver solution and then irradiating with 6.5?MeV electrons at different fluences varying from 1?×?10¹⁵ to 5?×?10¹⁵?cm^?2. Results of morphological and elemental analysis, carried out by Scanning Electron Microscopy and Energy Dispersive X-ray. Analysis revealed that the conical tracks could be fully filled with silver nanoparticles at electron fluence of 5?×?10¹⁵?cm^?2. The minimum d. c. resistance of an array of tracks, filled with silver nanoparticles and measured across the polyimide film, was orders of magnitude higher as compared to that of silver wires of equivalent sizes connected in parallel. In addition, these silver nanoparticles filled tracks exhibited rectifying I–V behavior and frequency dependent a. c. resistance, characteristic of metal–polymer nano-composites. Possible mechanisms have been discussed, which can justify the asymmetric current–voltage characteristics in such nano-composites.     

On the penetration of etchant into tracks in polycarbonate

The time dependence of the uptake of NaOH/LiOH etchant in pristine polycarbonate (PC) and in PC irradiated with 3 GeV Pb ions has been examined. Different stages of etchant penetration can be distinguished. The overall surface-near etchant uptake along tracks is always higher than the the one of the nonirradiated pristine material. Furthermore, the directional dependence of the etchant penetration during the incubation time is studied. Though the shapes of the etchant distributions along the tracks are practically the same in all directions, they differ in their absolute magnitudes. This can be explained by the different cross-sectional track areas exposed at the surface, which enable different etchant penetration efficiencies. Therefore, tracks which run more or less parallel to the surface normal show less etchant uptake than those being strongly tilted.     

Influence of silver on the Sm<Superscript>3+</Superscript> luminescence in “Aerosil” silica glasses

The introduction of silver into the samarium-containing silica glasses prepared by the original solgel method leads to the formation of complex optical centers involving samarium ions and simple and/or complex silver ions. These centers are characterized by the effective sensitization of Sm³⁺ luminescence by Ag⁺, (Ag₂)⁺, and (Ag⁺)₂ ions according to the exchange mechanism for, at least, Sm³⁺-Ag⁺ centers. The formation of Sm-Ag centers is accompanied by an increase in the concentration of nonbridging oxygen ions, which prevent the reduction of silver ions by hydrogen. Silver nanoparticles formed in small amounts upon this reduction are effective quenchers of luminescence from the corresponding excited states of Sm³⁺ ions.     

Influence of UV irradiation and heat treatment on the luminescence of molecular silver clusters in photo-thermo-refractive glasses

The luminescence spectra of photo-thermo-refractive (PTR) glasses containing cerium, silver, and antimony ions before and after UV irradiation and after heat treatment have been thoroughly investigated for the first time. It is shown that silver is present in the initial PTR glass in the form of ions and positively charged molecular clusters. After UV irradiation into the absorption band of cerium ions, silver partially passes to the neutral state in the form of atoms and neutral molecular clusters Ag₂, Ag₃, and Ag₄, which exhibit bright luminescence in the visible spectral range. Subsequent heat treatment at a temperature below the glassformation temperature leads to an increase in the luminescence intensity due to the increase in the concentration of neutral molecular clusters. Heat treatment at a temperature above the glass-formation temperature leads to the formation of silver nanocrystals and luminescence quenching. It is proposed to use PTR glasses with molecular silver clusters as phosphors for converting UV radiation into the visible range for solar power engineering and white LEDs.     

Preparation and characterization of conducting polymer/silver hexacyanoferrate nanocomposite

In this work, we present an alternative route to prepare silver hexacyanoferrate(II)/polyaniline (PANI) composite thin films. Differently from the electrochemical method, used to synthesize the conducting polymer film on a electrode surface, this new chemical route makes use of dialysis membrane as a solid support to synthesize the silver hexacyanoferrate(III) compound, and subsequently uses this composite membrane as oxidizing agent to polymerize the aniline monomer. The spectroscopic (UV-vis and IR region) and electrochemical characterization (cyclic voltammetry) indicates that the polymeric composite remains optically active and conductive. The X-ray analysis shows that the composite membrane/Ag₃[Fe_III(CN)₆] has an crystalline structure that can be assigned to the Ag₃[Fe_III(CN)₆] structure, and after reaction with aniline solution it became less crystalline. Additionally the SEM measurements shown that the reaction of silver ions with hexacyanoferrate(III) across the membrane results in a well defined and aliened Ag₃[Fe_III(CN)₆] crystals and when this crystalline compound reacts with aniline monomer silver wire of 100 nm of diameter by 6 μm longer are formed together with the conducting polymer polyaniline/Ag_x[Fe_II(CN)₆] composite.     

Electrolytes in etching of latent tracks of heavy ions in polyethylene terephthalate

Previously unknown features of etching of polyethylene terephthalate, latent tracks of multiply charged accelerated ions in it, and track membrane pore formation are considered. It was found that K ions (in the form of KCl salt) in a KOH solution enhance etching of both initial polyethylene terephthalate and tracks. Ba²⁺ ions enhancing etching of initial polymer significantly inhibit etching of tracks. It is assumed that etching inhibition is associated with Ba²⁺ ion adsorption on track active centers. The features detected are used to fabricate track membranes with thin selective layer.     

Percolation—related magnetic coupling and magnetoresistance properties in Fe／Si1—xAgx multilayers

In this paper, we present a study of the magnetic coupling and magnetoresistance (MR) properties in Fe/Si_1-xAg_x multilayers with a granular Si_1-xAg_x spacer layer. We have found that, with increasing silver content (x) in a silicon matrix, the magnetic state of multilayers changes from a nonmagnetic coupling state to weak antiferromagnetic around the percolation point of the ～2.4 nm thick spacer Si_1-xAg_x. The MR measurements also reveal an abrupt increase of MR near the same percolation point. These changes are ascribed to the formation of the percolation path in the granular spacer.     

Specific features of the luminescence of silicate glasses with silver introduced by ion exchange

The luminescence spectra of silicate glasses with silver introduced by ion exchange have been investigated. It is shown that silver introduced into glass by ion exchange exists not only in the form of ions, but also as neutral atoms and charged and neutral molecular clusters, which provide intense luminescence in the visible spectral range. Cerium ions in glass facilitate the formation of neutral molecular silver clusters, due to which the luminescence intensity increases. It is shown that Ag _n -Ce ^x+ complexes can be formed in glass containing cerium ions and neutral molecular silver clusters.     

The morphology control on the preparation of silver nanotriangles

A seed-mediated growth method was commonly applied to prepare one-dimension nanomaterials. However, some associated particles were unavoidable in the formation of target nanoparticles. Herein, we reported a modified method to prepare silver nanotriangles with higher uniform shape and particle size. The size and morphology of the formed nanoparticles could be controlled by regulating reaction conditions. The results showed that cetyl trimethyl ammonium bromide (CTAB) concentration and seed concentration were related with both the morphology and the particle size. The NaOH concentration, AgNO₃ concentration, and the mole ratio of V_c/Ag⁺ mainly affected the particle size of the formed nanotriangles. The formation of silver nanotriangles may be due to the selective stacking of the new tiny nanoparticles and the oriented growth of silver seed crystals. The oxidizing action of Br⁻/O₂ existing in the CTAB system should be responsible for the final morphology of truncated triangular silver nanoplates.     

Sensing and fluorescence behaviors of complex formation between new lariat crown ethers bearing fluorescence sidearm and metal ions in methanol solution

Fluorescence spectroscopic properties of the complex formation between six new C-pivot16-crown-5 ethers bearing fluorescence side arms and metal ions are studied. Six new C-pivot 16-crown-5 ethers that carry fluorescence side arms were synthesized. The research also included the examination of different fluorescent behavior of the new lariat ethers in the presence of silver and sodium ions (Ag⁺ and Na⁺) in methanol. Because of the good fit of the cavity size of these 16-crown-5 ethers with the Ag⁺ and Na⁺ ions, remarkable change in fluorescent spectra were observed. The results showed that the new lariat crown ethers exhibited enhanced selectivity towards sodium ion, but silver ion show quenching abilities towards the ligands. Cooperative participations of the C-pivot side arm oxygen with the ring oxygen molecules in complexation was also confirmed by the single crystal X-ray crystallography of the complex, (C₂₇H₃₀O₇)·NaClO₄. The freezing of crown ring conformation and the diminishment of the chance of sidearm oscillation that occurred upon complexation with sodium ion are the main causes of fluorescent enhancement. The quenching caused by the addition of silver ion was found to explainable by the photo-induced electron transfer that results in the reduction of silver ions.     

Evolution of magnetooptical and transport properties of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> films depending on silver concentration

Evolution of optical, magnetooptical, and transport properties of La_1?x Ag _x MnO₃/SrTiO₃ epitaxial films depending on the silver concentration (x = 0.05, 0.10, 0.15, and 0.25) is studied. The highest values of the Curie temperature (T _C ≈ 317 K), magnetoresistance (～16%), magnetotransmission (～8%), and transverse Kerr effect (δ ～ 20 × 10^?3) are attained for a concentration x = 0.10 of Ag⁺ ions. Comparison of the temperature dependences of the transmission of IR radiation, resistivity, magnetotransmission, magnetoresistance, and Kerr effect indicates electronic and magnetic inhomogeneity of the films in spite of saturation of films with silver. This feature of the film state is explained using the concepts of epitaxial stresses and metastable point defects.     

~(32)S离子辐照PET薄膜制备亚微米孔径核孔膜研究

使用中国原子能科学研究院HI-13串列加速器产生的32S离子轰击BOPET薄膜,薄膜在空气中陈化3个月后在专用装置中使用Na OH溶液蚀刻制备核孔膜,研究Na OH溶液浓度、蚀刻温度对微孔孔形的影响。在不同温度和蚀刻液浓度条件下,蚀刻出微孔孔径为0.2至0.93μm的亚微米核孔膜,计算其微孔锥角,得出微孔锥角随着蚀刻温度、蚀刻液浓度和微孔孔径的变化趋势。研究表明,采用低浓度、高温度的Na OH溶液蚀刻有利于减小微孔锥角,有利于制备较小孔径的核孔膜。如选用0.5mol/L的Na OH溶液浓度,在蚀刻温度为90℃的条件下蚀刻,此时蚀刻时间小于2 h,既可以得到高质量微孔膜也有利于提高生产效率。     

Chemical effects on x‐ray fluorescence yield of Ag+ compounds

X‐ray fluorescence measurements were carried out for silver metal and a number of silver compounds containing Ag⁺ ions such as Ag₂CO₃, Ag₂SO₄, AgNO₃, AgCl, AgBr and AgI using 59.6 keV γ‐rays, emitted from ²⁴¹Am, as the excitation source, to evaluate the value of Kβ/Kα x‐ray intensity ratio. For silver metal the value of this parameter is found to be 0.206 ± 0.003 and wide variations, 0.190 ≤ Kβ/Kα≤ 0.207, were observed for these compounds. The results are explained in terms of the charge transfer occurring between Ag⁺ and the coordinating anions. Copyright © 2005 John Wiley & Sons, Ltd.     

The statistical process of pore growth in multi pore foils

Using the electrolytical etching method the breakthrough-times (i.e. the time when the two etched cones from both sides of the detector contact) and the resulting track etching rates v_t of heavy ion tracks in 8 μm polycarbonate Makrofol KG have been measured. The samples were irradiated at the GSI, Darmstadt (Germany) with gold ions and different fluences at a specific energy of 11.6 MeV/u. All foils were etched in 6 n NaOH at room temperature. Fluctuations of breakthrough-times of single pore foils were analysed. Also the breakthrough-time of multi-pore-foils were measured. The dependence of the mean breakthrough-time on the ion fluence is dicussed. This dependence will be explained by the fluctuations of the breakthrough-time of the pores.     

Self Assembly of the Metal Nanoparticles: Formation of the Highly Oriented,Core-Shell Type,Bimetallic Gold–Silver Film

A synthetic route is presented for the preparation of a bimetallic gold–silver film under UV-irradiation. Methoxy polyethylene glycol, a water soluble polymer, is used as the reducing agent for the gold and silver ions in the presence of a ultra-violet source that results in the formation of gold and silver bimetallic nanoparticles. During stirring a centrifugal force is generated at the center of the solution, which results in a coalescence of the nanoparticles and forms a self-assembly of small subunits that ultimately produces a film-like network. UV–vis spectra and scanning electron microscopy were used to determine, respectively, the configuration of the gold and the silver in the nanoparticles, a Au_core–Ag_shell structure, and the thickness of the film.     

Dissociation channels of silver bromide cluster Ag<Subscript>2</Subscript>Br,silver cluster Ag<Subscript>3</Subscript> and their ions studied by using alkali metal target

Various dissociation channels of silver bromide cluster ion Ag₂Br⁺ and silver cluster ion Ag₃ ⁺ were observed in high-energy collisionally-activated dissociation (CAD) using a Cs target. The fragment patterns of the high-energy CAD were compared with those of the metastable dissociation and low-energy CAD. The difference in the fragment patterns between the high-energy CAD and the other dissociation methods was explained in terms of the internal energy distributions. The dissociation mechanisms of neutral silver bromide cluster Ag₂Br and silver cluster Ag₃ were also investigated by charge inversion mass spectrometry using the Cs target. While the fragment ions AgBr^- and Ag₂ ^- were dominantly observed in the charge inversion spectrum of Ag₂Br⁺, the undissociated ion Ag₃ ^- was observed as a predominant peak in the case of Ag₃ ⁺. The dissociation behavior of Ag₂Br^* can be explained on the basis of the calculated thermochemical data. Contrary to this, the predominant existence of the undissociated Ag₃ ^- cannot be explained by the reported thermochemical data. The existence of undissociated Ag₃ ^- suggests that the dissociation barrier is higher than the internal energy of Ag₃ ^* (theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization potentials of Ag₃ and Cs.     

Metastable fragmentation of silver bromide clusters

The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag_nBr_{n - 1} ⁺ and Ag_nBr_{n + 1} ^- and Ag₁₄Br₁₃ ⁺ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag_nBr_{n - 1} ⁺ is no more the main series, and Ag_nBr _{n - 2, 3} ⁺ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag₃Br₃ cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag⁺-Ag⁺ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)₃ and to quasi-planar cyclic structures of (AgBr)_n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)_n, and to cuprous halide compounds. Received 9 November 2000 and Received in final form 25 January 2001