The pore opening process and its influence on conductivity measurements of irradiated polymer films by application of the electrochemical etching method

The technique of the electrochemical etching of irradiated polymer films is an useful method to investigate structures of the track cores.

The transversale etching rate as a function of the radius, derived from the time-dependence of the radius of the etching pore, can be interpreted as a corresponding magnitude of the degree of the damage within the track core.

In the case of polymer films irradiated by a high track density, the influence of the time distribution of the breakthroughs (pore opening process) of the etching microchannels on the conductivity changes during the etching process is to be discussed. First represented results lead to statements about the statistical nature of the pore opening process.     

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.     

Design of a multifoil electrolytically controlled etching cell

Irradiating polymer films with heavy ions and subsequent electrolytically controlled etching (ECE) produces nuclear track filters with desired pore dimensions and pore density. During ECE, an electric field with low field strength and a frequency in the audio range is applied across the irradiated polymer film, which is immersed in the etching solution. An ECE cell for the simultaneous etching of three irradiated samples has been designed and developed. The average pore diameter and break-through time for tracks due to ²³⁸U(11.4 and 14 MeV/u) and ²⁰⁹Bi(13 MeV/u) ions in polycarbonate and polyethylene terepthalate have been measured.     

Modeling the fission track etching process in apatite: Segmentation or crystallography influence

In this study, two factors which can influence fission track etching in apatite are considered: track segmentation (induced by thermal annealing) and variable radial etching speed (due to the reagent diffusion during the etching process).

During the latent track annealing, two distinguishable steps can be identified by measuring track lengths or diameters. A length reduction is firstly observed, followed by a segmentation process which leads to the emergence of disrupted regions (gaps).

At present time, electron microscopy studies on fission tracks in apatite show profiles which lead to hypotheses of a variable radial etching speed versus depth. These variations can be interpreted in terms of acid diffusion along the track. Moreover, the existence of several bulk etching speeds related to crystallographic orientation is approached.

Taking into account these different points, a software program, integrating parameters as original track orientation and depth, number of gaps, etc., is developed in order to model the track profile evolution during the etching process. Comparison with experiments in Durango apatite (Mexico) are also undertaken.     

Evolution of the polyethylene terephthalate track membranes parameters at the etching process

A comprehensive study of parameters of the track membranes based on the polyethylene terephthalate has been carried out at different formation stages. Using the X-ray diffraction analysis, the changes in the structure of the polymer after its irradiation, UV-sensitization and etching are shown. By means of scanning electron microscopy, a sequential analysis of the variation of the parameters of the track membrane during the etching has been carried out, based on which the evolutions of surface morphology and pore sizes are shown.     

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.      

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.     

Funnel-type etched ion tracks in polymers

It is shown that conical track etching is a much more complicated process than generally assumed. The choice of the corresponding parameters (i.e. the ratios of concentrations and diffusion coefficients of both etchant (e.g. NaOH) and stopping solutions (e.g. HCl) and the etching temperature) determines the ratio of polymer dissolution to etchant penetration. The latter value controls the counterplay of diffusion, etching, ionic conductivity, field emission and capacitive effects, which is decisive for both the final track shapes and their electronic properties. The stages of track evolution during etching under different conditions are outlined in detail. Both transparent conical nanopores and “funnel-type” tracks can be obtained, the latter consisting of a shorter cone and a residual latent track. Depending on the internal structure of that latent track segment, such funnel-type tracks either allow smooth transmission of the rectified currents or they emit unipolar current spikes. Not only the study of electronic properties of single ion tracks, but also of a multitude of tracks makes sense. Depending on the applied parameters, the individual track properties may either just add up, or new effects may be found that emerge from the interaction of the tracks among each other. This is preferentially the case for spike-emitting tracks, where effects such as phase-locked spike synchronization can be found as described by neural network theory.     

The influence of etching parameters on the sensitivity of plastics

Abstract

It seems that the critical rate of primary ionization for track registration must also depend on the etching conditions. Simple experimental methods are presented to show a possible change in registration sensitivity as a function of the chemical parameters. It was proved, from investigations of α-particle tracks, that the sensitivity of a cellulose acetate detector can considerably depend on the concentration and type of etching reagent. Quantitative data are given on the ratio of the rate of chemical etching along the track and on the detector surface as a function of concentration of NaOH solution for tracks of fission fragments registered in plastics of cellulose acetate, polycarbonate and polyethylene-terephthalate.     

Fission fragment track etching modelling for the cellular localisation of Neptunium-237 nuclei in rat tissues

Heavy ion recording in dielectric isotropic detectors has a wide range of applications in uranium cartography or dating. In this study, solid state nuclear tracks detectors (SSNTDs) have been applied to localise neptunium-237, in vivo, by means of the neutron-induced fission cartography of neptunium-237 nuclei in organ sections. At the cellular level, a precise localisation can only be achieved with a good understanding of the etch pit evolution during the chemical etching process.

A tailor-made software for modelling the etching process has been developed to simulate the profile of an etched track produced by a neutron-induced fission fragment. This software is based on a model that considers the evolution of the track etching velocity along the damage trail in order to perfectly model the shape of the track.     

Latent track structure in polymers as observed by a highly sensitive electrolytical conductivity measurement

Abstract

First results of a new electrolytical conductivity cell are reported concerning the initial stage of the pore opening process during track etching in vitreous solids. On the basis of the soft mode (low-energy excitation) model for track etching, a distribution function for the number of perforated micropores as function of time is calculated by accounting for the radial etch rate as function of the effective pore radius.     

Energy loss dependent transversal etching rates of heavy ion tracks in plastic

By the method of electrolytical etching track etching rates V_t and corresponding transversal track etching rates V_trans of single heavy ion tracks in thin Makrofol KG foils have been measured at ion energies from 10–480 MeV/u. Makrofol KG foils of 8 μm thickness were irradiated perpendicular to the surface with ⁷⁹Au and ⁵⁴Xe ions at specific energies with energy loss values of REL=(10–90) ^*10³ MeVcm²/g at GSI Darmstadt, Germany, and Lawrence Berkeley Lab., Cal., USA. Using the electrolytical etching method by measuring the resistance of the foil during the etching process (etching conditions: 6n NaOH, room temperature and controlled 50° C) the breakthrough time and track etching rates V_t, V_trans and V_m (bulk etching rate) were analysed. Response curves (V_t/V_m)-1 as a function of Restricted Energy Loss (REL), the maximum extension of the ion induced damage perpendicular to the ion path and the dimension of the ion track core depending on the deposited energy can be estimated.     

Effect of thermal annealing on pore density,pore size and pore homogeneity of polycarbonate NTFs

When an energetic and electrically charged beam of particles penetrates a nonconducting material, like crystal, polymer, etc., a permanent change in the nature of the chemical matrix along its path occurs giving rise to damaged sites known as latent tracks having diameter of the order of 10 nm. These tracks show an enhanced chemical reactivity as compared to the surrounding material; and, on etching, the damaged sites are enlarged forming nuclear track filters (NTFs). The NTFs so formed find applications in the fields as nuclear physics, geology, radiation dosimetry, material research, medicine and environmental studies. The pore density and pore size homogeneity are important traits of NTFs. These NTFs are also employed for the production of micro/nanostructures through template synthesis which finds various applications for the fabrication of sensors, devices and in the field of opto-electronics. The pore size of the NTF is generally not uniform due to various reasons like material defects in solid state nuclear track detectors (SSNTDs), nonuniform flux density of irradiating beam, variation in the angle of exposure during irradiation, temperature gradient in the etching solution, etc. The present work reports the development of NTFs and study of the effect of pre-etch thermal annealing of irradiated polycarbonate thin films (SSNTDs) on the density and homogeneity of etched pores in developed NTFs. NTFs were developed by irradiating Makrofol (KG) with heavy-ion beam at the UNILAC, Gesellschaft fur Schwerionenforschung (GSI), Darmstadt, Germany and then chemically etching of annealed and unannealed irradiated samples. The pore size, pore density and pore size homogeneity of the NTFs were compared for annealed and unannealed samples. The study indicates decrease in pore size, pore density and increase in homogeneity of pores with post-irradiation and pre-etch thermal annealing. The uniformity of the pores of NTF will lead to uniformity of micro/nanostructures fabricated by using the pores as templates. These uniform micro/nanostructures can act as excellent charge sprayers in the cold cathode emitters.     

Conductivity of aged non-overlapping and overlapping tracks in ion irradiated polyimide

Non-overlapping as well as overlapping tracks of energetic ions have been introduced into polyimide foils. After aging their conductivity was measured. This — to our knowledge — first systematic study shows that conductivity does not only result from multiple track overlapping, but can be found already in single ion tracks. This conductivity is shown to be primarily a consequence of electronic energy transfer. The conductivity of single ion tracks is higher than that of typical insulators, but still orders of magnitude lower than that of typical semiconductors. The conductivity is independent of the applied electric field strength until at excessive voltages the electric current increases nonlinearly up to complete breakthrough. The total conductivity of an irradiated polyimide foil increases proportionally with ion fluence for large ion track spacings, and approaches saturation when the electronically active track regimes begin to overlap. Above some thousand times track overlapping however, new chemical and structural changes in the irradiated material lead to another strong increase in conductivity.     

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.     

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.     

基于智能算法的CR39径迹刻蚀过程模拟

CR39可以用于激光等离子物理实验中的离子探测,并给出离子数目、种类和能量信息。通过采用唯象模型,利用离子在CR39中径迹形成的阻止本领动力学方程以及粒子群智能算法对径迹形成的过程进行了数值化模拟,研究了CR39中离子径迹在刻蚀过程中的演化过程,获得了入射离子能量和径迹直径、深度的对应关系,并且发现当离子射程与刻蚀深度相等时,径迹深度最大,给出了利用总刻蚀时间计算最大径迹深度对应的临界能量的公式。     

Pushing the limits of macroporous silicon etching

We present a detailed investigation of the fabrication of almost perfect three-dimensional microstructures grown by a photoelectrochemical etching process. The focus is directed on the physical effects that have limited the achievable pore shapes to very smooth modulations. These limits can be overcome by an improved etching process allowing strongly modulated three-dimensional networks. In particular, the chronology of the growth of a single modulation is shown. PACS 82.45.Cc; 82.45.Vp     

Characterization of nuclear tracks by positron annihilation and gas permeation

The application of polymeric membrane in combination with metallic films can be used for gas purification in particular for hydrogen where the molecular size is very small. The affinity of hydrogen to certain metals assists the flow of hydrogen, although it restricts the permeation of other gases. However, the flow rate is very small in dense membranes. Attempts have been made to generate nuclear tracks in polymeric membranes to control the gas flow. These tracks can be characterized by positron lifetime spectroscopy and gas permeation measurements. The long lifetime of ortho-positronium gives the estimate of size of the track-free volume of the order of 0.25 nm. The nuclear tracks can be modified by a chemical etching process. The chemical etching normally takes place from both sides of the membrane. When the etched pits from both sides meet, a rapid increase in gas permeation is observed. The size of the nano opening of the track has been observed for two different gases hydrogen and carbon dioxide, which have a molecular size of 0.2 and 0.4 nm, respectively.