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.     

Morphologies of latent and etched heavy-ion tracks in {111} CaF2

Structure details of latent tracks created by U, Pb and Au ions (energies 6.9, 28.7 and 11.1?MeV/A, respectively) in {111} CaF₂ have been extracted by means of scanning force microscopy and transmission electron microscopy. The revealed structure has assisted in the interpretation of the etching behaviour of tracks created in {111} CaF₂ by 9.2?MeV/A Bi ions. In the latter experiments, irradiated fragments were immersed for short durations in a 3:1 10% HCl/96% H₂SO₄ solution and the morphology of the formed etch pits was derived by high-resolution scanning electron microscopy and scanning force microscopy. Three conclusions emerged. First, ion-induced surface hillocks exhibit no resistance against etchant attack. Second, the primary etching diameter of the track coincides with the nanometric width of the structurally altered track core. Third, the structure of the etch pits, 3-faced symmetric pyramidal depressions with {122} faces, indicates that etching across the track halo, a few tens of nanometers wide strained crystal, is dominated by surface energies of crystal faces.     

The chemical etching of fission fragment tracks in natural fluorite

An experimental study of the mechanism for chemical etching of fission fragment tracks in the natural mineral fluorite is described. A systematic search showed that a 3:1 mixture by volume of sulphuric to hydrochloric acids was a most appropriate etchant. Experiments directed at determining the etching efficiency as a function of solvent temperature are also discussed. The preferential track etch ratioVt/Vg, the track length and the track density all depend upon the time and temperature of annealing.

It is variations of the fission track density in fluorite, with etching time and annealing temperature, which make possible an overall geophysical interpretation of annealing data for the mineral in terms of the paleoisotherm of its intrinsic fission track clock.

An interactive image analysis system INTIMAN, assembled for the swift and automatic readout of fission fragment track measurements, in both crystalline and non-crystalline materials, is described. Normal procedures for measuring and analyzing tracks are outlined.     

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.      

Conducting swift heavy ion track networks

In this paper, the electronic behavior of conducting swift heavy ion track networks is studied. On the one hand, the transient conductivity of ion tracks in metal oxides on silicon in status nascendi is exploited for this purpose, and on the other hand, conducting tracks are produced by ion irradiation of insulating membranes (either self-supported or deposited onto silicon substrates), subsequent etching and finally inserting conducting materials of whatever provenience (in this work preferentially electrolytes). Depending on their manufacture, the conducting tracks either act as electronically active or passive elements. When applying a voltage across individual tracks in the first case, one observes current spikes with negative differential resistances. These tracks interact among themselves, leading to phase-locked synchronous coupled oscillations with complex patterns that are quite similar to those emerging from neural networks. The other case corresponds to networks of electronically passive conducting tracks which become overall electronically active only through their collective interactions. Though the aforementioned effects had been experimentally described earlier, they are re-visited here to make clear that the corresponding systems have to be considered as being artificial neural networks. On this occasion, some new findings are added.     

Application of a cellular automaton for the evolution of etched nuclear tracks

In the present work, it is demonstrated the first application of cellular automata to the growing of etched nuclear tracks. The simplest case in which conical etched tracks are gradually formed is presented, as well as a general case of time varying etching rate V_t. It is demonstrated that the cellular automata elements consist in an image pattern of the latent nuclear track input cells, 16 rules for updating states, the Moore neighborhood and an algorithm of four states.     

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.     

Ion track etching revisited: II. Electronic properties of aged tracks in polymers

We compile here electronic ion track etching effects, such as capacitive-type currents, current spike emission, phase shift, rectification and background currents that eventually emerge upon application of sinusoidal alternating voltages across thin, aged swift heavy ion-irradiated polymer foils during etching. Both capacitive-type currents and current spike emission occur as long as obstacles still prevent a smooth continuous charge carrier passage across the foils. In the case of sufficiently high applied electric fields, these obstacles are overcome by spike emission. These effects vanish upon etchant breakthrough. Subsequent transmitted currents are usually of Ohmic type, but shortly after breakthrough (during the track’ core etching) often still exhibit deviations such as strong positive phase shifts. They stem from very slow charge carrier mobility across the etched ion tracks due to retarding trapping/detrapping processes. Upon etching the track’s penumbra, one occasionally observes a split-up into two transmitted current components, one with positive and another one with negative phase shifts. Usually, these phase shifts vanish when bulk etching starts. Current rectification upon track etching is a very frequent phenomenon. Rectification uses to inverse when core etching ends and penumbra etching begins. When the latter ends, rectification largely vanishes. Occasionally, some residual rectification remains which we attribute to the aged polymeric bulk itself. Last not least, we still consider background currents which often emerge transiently during track etching. We could assign them clearly to differences in the electrochemical potential of the liquids on both sides of the etched polymer foils. Transient relaxation effects during the track etching cause their eventually chaotic behaviour.     

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.     

Nuclear tracks in solids: registration physics and the compound spike

Observations of GeV heavy ion and MeV cluster-ion tracks in crystalline solids give us new insight into registration physics. Thermal and ion explosion spikes no longer compete; a ‘compound spike’ accounts for both. Ion explosion dominates for surface tracks (electronic sputtering). And there can also be transient plasma stopping in the bulk. For clusters there are ‘vicinage effects’—both electronic and nuclear—which can influence track dimensions and structure. Displacement cascades in large energetic clusters may lead to projectile “fission” and coherent flow into sub-tracks. The absence of tracks in certain targets, and their size/structure in others, leads to a model of projectile assisted prompt anneal (PAPA) in 10⁻¹¹s, either partial or complete, often by swift epitaxy, on elemental lattices (e.g. silicon) or on compound sublattices (e.g. fluorite). Phase transformations are important, but simple target amorphization is rare—the exception, not the rule. For many targets the thermal spike (macroscopic) fails, since ‘point’ defects (atomistic) characteristic of the target, their motion, and the electronic band structure, determine latent track detail. Circumstances in which the Bragg Rule of Additivity fails completely are revealed, and the kinetic threshold for constructive phase transitions in tracks described. This same track physics applies generally also to geothermometry—the opposite time extremum (10⁺¹¹s)—where annealing is due to defect assisted delayed anneal (DADA). Differences between etching rates of induced and spontaneous fission tracks can be explained. The geothermobarometric “Wendt/Vidal effect” (2002)—combined pressure, temperature and stress (with time) influences on fission track annealing (in e.g. apatite)—is briefly discussed.     

Electrical current pulsations through ion irradiated polymer foils in electrolytes

Funnel-type ion tracks were produced in thin polymer foils by swift heavy ion irradiation and subsequent treatment with both low concentration etchants and acids from two different sides. The funnel shapes consist of shallow etched cones and residual latent tracks and thus combine both their characteristic properties, rectification and current spike emission, in one track each. Arrays of spike-emitting tracks are known to exhibit phase-locked synchronous electrical pulsations in accordance with the neural network theory. These pulsations were studied here on arrays of funnel-type tracks for the first time. As expected, the results strongly depend on the track density. In foils with low track densities, synchronous oscillations are rare and rather unstable events, whereas foils with high track densities exhibit stable, strong and long-lasting pulsations. Insertion of 0.1 M KCl solution into tracks at low density improved the shape and regularity of the spuriously occurring spikes somewhat, as compared with water in these tracks.     

Track structure in polyethylene terephthalate irradiated by heavy ions: Let dependence of track diameter

The structure of latent tracks in polyethylene terephthalate is studied using chemical etching combined with a conductometric technique. Geometrical parameters of the latent tracks for the range of the electronic energy loss (dE/dx) between 3 to 24 keV/nm are estimated. The dependence of the track core and track halo size on the energy loss is analyzed.     

Different shapes of tracks in phlogopite, biotite and soda lime glass

Etched track opening geometries in Biotite, Phlogopite and soda-lime glass irradiated with swift heavy ions [¹⁹⁷Au(11.64 MeV/n), ¹³⁶Xe(11.56 MeV/n), ⁵⁸Ni(11.56 MeV/n)] at different angle of incidence have been studied using appropriate chemical etching technique. Different geometries (Hexagonal, irregular polygon, triangular in case of Biotite and Phlogopite, and circular & elliptical in case of soda lime glass detector) of heavy ion tracks are reported in the present investigations using optical microscope. The different shapes of these heavy ions track geometries are found to be related with various target-projectile parameters (viz: type of projectiles, energy, stopping power, angle of incidence of the projectile, density of defects and its reactivity with etchant, etching conditions and chemical structure of the detectors). The dependence of different shapes of heavy ion tracks in isotropic and anisotropic medium on the variation of radiation damage densities along the ion trajectories have also been discussed in the present paper.      

Track recording properties of soda glass detector for accelerated heavy ions

The etch pit diameters of soda glass detector samples exposed to ₅₄ ¹³² Xe-ions of different energies are measured for different etching times after etching the detector in a ‘new etchant’ free of the adverse effect of the etch product layer. The dependence of track diameter on the energy and on the energy loss, dE/dx of ₅₄ ¹³² Xe-ion in soda glass has been presented. The energy resolution of soda glass and the critical angle for etching of fission fragment tracks in glass detectors have also been determined. The maximum etched track length of ₅₄ ¹³² Xe-ion in soda glass has been compared with the theoretical range. The effects of different annealing conditions on bulk etch rate of glass detector and on diameters of ₅₄ ¹³² Xe-ion tracks have been presented. Experimental results show that there is a decrease in track etch rate, etching efficiency and etchable range of ₅₄ ¹³² Xe-ions with annealing. The annealing of oblique tracks shows that the vertical tracks are more stable than the oblique tracks.     

Etchability of Latent Fission Fragment Tracks in CR-39

We report the chemical etching behaviour of the CR-39 polymer detector exposed to fission fragments of 252Cf describing etchability of latent tracks, which are like nanocylinders. The fission fragment exposed detectors were etched in 1-7 N NaOH water solutions at temperatures 50-80℃ for 45 min in the case of track length and 180 min in the case of track diameter measurements. The reduced etch rate S （called here etchability） is determined using experimental results for all etching conditions and the etching conditions with the highest reduced etch are obtained. Physics and energetics of bulk and track etching are discussed. Possible effects causing spurious changes in determination of activation energy of etching are investigated.     

Investigation of latent and short etched heavy ion tracks in solids

In the past five years were carried out SANS (Small-Angle Neutron Scattering measurements in the JINR to investigate latent and short etched tracks in SSNTD. The results demonstrate the suitability of the method to study not etched and short etched tracks to analyse the etching process, e.g. for nuclear track filter production. The results are in good agreement with other methods as conductivity measurements.     

Swelling and structure of radiation induced near-surface damage in CR-39 and its chemical etching

Systematic measurements of swelling of CR-39 nuclear track detector (NTD) due to irradiation with fission fragments and alpha particles over a wide range of fluences from ²⁵²Cf are presented here. Precisely designed and optimized exposure and chemical etching experiments were employed to unfold the structure of radiation induced surface damage. Delays in the startup of the chemical etching of latent tracks in low radiation fluence detectors are measured and are found to contain important information about structure of the surface damage. Simple atomic scale pictures of radiation induced surface damage and its chemical etching are developed using measurements of radiation induced swelling of CR-39 detectors and nuclear track parameters. The computer code SRIM2010 was utilized for the calculations of basic features of latent tracks of fission fragments and alpha particles in CR-39. Another computer code TRACK_VISION was used to compute parameters of etched tracks. Computations and experimental findings in the paper coherently compose a realistic picture of radiation damage.     

Formation of ion damage tracks

The formation of damage tracks in insulators from the passage of energetic (MeV/amu) ions indicates that the energy lost by an ion to electronic excitation is partially transferred to atomic motion. It is known that a track consists of localized regions of extended defects that are separated by lengths that exhibit only point defects. The utility of tracks for selective detection of various types of ions arises because of preferential chemical etching along the track as compared to etching the bulk material. In this letter we propose a new model to explain both the localized damage regions and the preferential etching of damage tracks. The formation of each region of extended defects is initiated by the Auger decay of a vacancy produced in an inner electronic shell of an atom of the insulator by the incident ion. This decay produces an intense source of ionization within a small volume around the decaying atom, which causes decomposition of the material in a manner similar to that observed in pulsed laser irradiation. The resulting chemical or crystalline modification of the material is the latent track, which because of its changed structure can be preferentially etched.     

The electron spin resonance of polycarbonate track detectors

Polycarbonate films are widely used as solid state track detectors (SSTDs) of radiation, but as yet our knowledge of the microscopic nature of the latent track is limited. The processes of chemical etching and thermal annealing are not fully understood. The lack of stability of track parameters bears on the accuracy of the charge determination of energetic heavy nuclei.

We have applied the technique of electron spin resonance, (ESR) in order to seek a correlation between the density of tracks and the growth and decay of free radicals detected by ESR. Samples of polycarbonate were irradiated with thermal neutrons and then etched progressively with NaOH. The ESR signal increased initially and then became weaker as the bulk of the polycarbonate was removed. Other samples were annealed after partial etching. ESR monitoring of this annealing showed that free radicals were recombining, probably due to diffusion processes.     

On the formation of heavy ion latent tracks in polymeric detectors

Three kinds of polymeric track detectors have been examined by ESR spectroscopy following heavy ion or energetic electron bombardment: (1) Typical nuclear track detectors: makrofol, kapton, terphane; (2) Polymers whose radiolysis under γ-rays or electron beams is well established: PMMA, PE, PP; (3) Polymers in which etchable tracks have not so far been observed e.g. teflon. The influence on the various ESR spectra of the radiation dose, of annealing or chemical etching treatments leads us to suggest that existence of heavy ion latent tracks might be correlated with the formation of “carbon-like” radicals such as produced in polymer pyrolysis.