High sensitive electrolytical conductivity measurements of irradiated polymer films of 1μm thickness measured by a modified experimental set-up

The interaction of heavy ions with solids produces a narrow radial core of primary damage. The actual nature of the damage and the mechanism of its formation is not yet fully understood.

The technique of the electrochemical etching of irradiated samples is an useful method to investigate these 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 the corresponding magnitude of the degree of the damage within the track core.

To carry through measurements of smallest radii of etching pores, their very high electric resistance respectively, a sophisticated experimental set-up is required.

An advanced set-up is performed, which enables, by application of a combined d.c.-a.c.-method, to measure the resistance of the sample during the whole etching process, associated with the origin of pore and its growth up to radii of 10 nm and more.     

The pore opening process of etching polymer films irradiated by single and multiple heavy ions. The etching process in the range of the track core radius (10 nm)

The technique of electrochemical etching of irradiated polymer films is an useful method to investigate structures of the track cores. In the case of the investigation of multiple track foils, the mean effective radius corresponds to the average of all synchron etching pores. On the other hand, the etching cones of all tracks do not break through to conducting micro channels coincidentally. The statistical character of this pore opening (break through) process is still unexplained, although several effects concerning this topic have been observed in the past. Another computer program simulates by way of the Monte Carlo Method the etching process of an ensemble of tracks within a thin polymer film. The conductivity of the multiple track etching foil can be described by the convolution between the conductivity of a single pore and the time dependent breakthrough rate. By way of the Laplace Transforms the measurements of the multiple and single track etching polymer films can be deconvoluted and yield the statistical nature of the pore opening process.     

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.     

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.     

Comparison of responses of CR-39, PM-355, and CN track detectors to energetic hydrogen-, helium-, nitrogen-, and oxygen-ions

Samples made of the CR-39 and PM-355 plastic nuclear track detectors (NTDs) as well as of the CN films were irradiated with quasi-monoenergetic beams of protons, alphas, N⁺-, and O⁺-ions produced by various accelerators. For different samples an energy value of the particle beams was changed from several hundreds keV to 3 or 4.5 MeV. After irradiation the detector samples were etched chemically under controlled conditions during periods lasting from 2 hrs to 20 hrs. Every 2 hrs track diameters were measured by means of an optical microscope. Differences in the crater diameters in the detectors etched in steps, and those etched continously, have been found to be smaller than 10 percent. The paper results detailed calibration diagrams showing a dependence of track diameters on the ion energy value for different etching times.     

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.     

Heavy-ion particle spectrometry by track pattern in muscovite detectors

Muscovite mica detectors were irradiated with the ions: ¹⁹F of 47.5 MeV, ²⁴Mg of 57 MeV, ²⁸Si of 28 and 74 MeV, ³²S of 32 and 74 MeV, ⁶³Cu of 78.75 MeV and with neutron induced uranium fission fragments. Using optical microscopy, after an appropriate chemical etching, two characteristic etched track structure patterns were observed: a rhombic pyramid terrace structure for the Mg, Si and S ions, and a rhombic prism structure for the Cu ions and fission fragments. The use of these etched track patterns to discriminate two groups of ions between them, for the energy range covered in this work, is proposed.     

Optimization of the heavy nuclei track etching in olivine crystals from meteorites

The investigation of the track etching velocity dependence for nuclei with Z50 on pH of the etching solution in the olivine crystals from Marjalahti and Eagle Station meteorites, containing galactic cosmic-ray nuclear tracks and also the crystals from Marjalahti meteorite, calibrated at the UNILAC (GSI, Darmstadt) with 14.17 MeV/N ²⁰⁸Pb nuclei, were performed.

The pH of the etching solution were changed from 7.8 to 9.4. It is shown that the optimal track etch condition were realised at pH of etching solution in the interval from 8.4 to 8.8.

The results of the Galactic cosmic-ray nuclei tracks with Z83 revealed in olivine crystals are presented. They were additionally irradiated at 90% to the surface with accelerated 14 MeV/N ¹³²Xe nuclei.     

Damage morphology of Kr ion tracks in apatite: dependence on dE/dX

With the aim of characterizing damage along nuclear tracks in apatite, Durango fluoroapatite monocrystals were irradiated under a high fluence ⁸⁶Kr ion beam at the G.A.N.I.L. (Grand Accélérateur National d'Ions Lourds, Caen, France). The resulting irradiation damage was studied by associating CRBS spectrometry and chemical etching. By applying Poisson's law to the backscattering results, the nuclear track average effective radius R_e was calculated for different steps along the ion path. On the other hand, the chemical etching experiments allowed us to deduce three different damaging morphologies in correspondence to the R_e values. For the first time in apatite, it has been shown that a defect fragmentation produced along the ion paths may be detected by chemical etching. These results were also applied to fission tracks in order to quantify the damage rate and to describe the damage morphology evolution along fission fragment paths.     

纳米孔径核孔膜的制备研究

高能硫、氪、氙离子轰击聚酯(PET)和聚碳酸酯(PC)膜后,对样品进行陈化和紫外线照射敏化.用电导法着重研究蚀刻条件对样品的归一化径迹蚀刻速率(灵敏度)的影响,结果表明优化条件下灵敏度较通用条件下提高约2倍,PET的灵敏度可达1000,PC的灵敏度可达2000,可以用于制备纳米孔径核孔膜.核孔膜中填充的铜纳米线的电镜照片显示出纳米线最小直径为20nm.用电导法计算纳米孔的孔径,该值与纳米线直径的电镜测量值在孔径大于30nm时符合良好.     

Sensitization of polymeric track detectors with carbon dioxide

The effect of CO₂ on the sensitivity of polymeric track detectors was studied. It has been found that the sensitivity of SR-90 is dependent on the amount of CO₂ dissolved in the polymer at the time of etching. It has been also found that CR-39 can be sensitized to some extent with an aging in CO₂. Since the sensitization in CO₂ is possible even a long time after the irradiation, the mechanism of the latent track formation by CO₂ is quite different from that by O₂. This would be the key to achieve the long term stability of polymeric track detectors such as SR-90 and CR-39.     

Investigations of heavy ion tracks in polyethylene naphthalate films

The heavy ion beam (with fluence 3x10⁸ ion/cm²) from a cyclotron has been used for irradiation of thin polyethylene naphthalate (PEN) films. Latent tracks in these polymeric films have been sensitized by UV radiation and then chemically etched in NaOH solution. The etching process parameters have been controlled by the electroconductivity method. After etching, parameters of samples have been examined by SEM and bubble point methods (Coulter® Porometer II instrument). Results have shown good quality of PEN track membranes with pore sizes in the range: 0.1 – 0.5 μm. The described procedure is known for thin polythylene terephthalate (PET) films. Taking into consideration that PEN films have got better mechanical, thermal, gas barrier as well as better chemical resistance properties in comparison with PET films, the possibility of application of such membranes is much wider.     

Studies on the nuclear tracks in CR-39 plastics

A review was given for our recent studies on the latent tracks in CR-39 nuclear track detector. The radial size of track core has been determined through UV spectral measurements combined to the model of track overlapping and by AFM observations of slightly etched detectors. The track core radius was found to be about a few nano-meters and almost proportional to the cubic root of stopping power. As a control study, the etching properties of CR-39, irradiated by low-LET radiation, has been examined. The observed depth dependence and dose-rate dependence of the bulk etch rate of the irradiated CR-39 were explained that the damage formation process was governed by the reaction between the radiation induced radicals and the oxygen supplied from the air. This indicated that latent tracks in CR-39 are produced through local radiation induced oxidation process along the ion paths. Studies on vibration spectra, near-IR, FT-IR and Raman spectra, of CR-39 have also been carried out to estimate the chemical structure of the latent tracks. The creation of OH group in irradiated CR-39 has been confirmed.     

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.      

Modifications in track registration response of PADC detector by energetic protons

It has been well established that different ionising radiations modify the track registration properties of dielectric solids. In an effort to study the response of Polyallyl diglycol carbonate (PADC Homalite) detector towards fission fragment, PADC detectors were exposed to 10⁴ Gy dose of 62 MeV protons and then one set of samples were exposed to fission fragments from a ²⁵²Cf source. Two of these detectors were containing a thin layer of Buckminsterfullerene (C₆₀). The study of the etched tracks by Leitz Optical Microscope reveals that the track diameters are enhanced by more than 70% in the proton irradiated zone as compared to that in the unirradiated zone. Scanning Electron Microscopy was performed after etching the sample in 6 N NaOH at 55°C for different etching times, to study the details of the surface modifications due to proton irradiation of PADC detectors with and without C₆₀ layer. Our observations revealed that the diameters and density of proton tracks have increased with etching time on the surface facing the fullerene layer as well as the other surface. However, a relatively more open structure of the etched surface containing C₆₀ as compared to the bare one may be an indication of the extra damage caused by the energy released upon the destruction of C₆₀ molecules by energetic protons.     

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.     

Studies on the track formation mechanism of the heavy ions in CR-39

The bulk etch rate for two types of CR-39 detector was measured as a function of temperature and the activation energies of bulk etching was determined. Experimental values of track etch rate were derived directly from the function of the succesive measured track length vrs. etching time for ²⁰⁹Bi, ¹²⁹Xe and ²⁰Ne ions.

The maximum etchable length of 13 MeV/u ²⁰⁹Bi and 13.04 MeV/u ¹²⁹Xe ions have been measured at and below these energies. A comparison of the measured and calculated track length data is presented.     

Determination of the range of alpha particles in SSNTD by optical density method

A technique based on the optical density (D) measurement of the etched track is useful for charged particles spectroscopy using SSNTD. It was shown that the stopping power of alpha particles in CR-39 is proportional to D. We measured the optical density and derived an expression to estimate the range of alpha particles in CR-39 detector as a function of the bulk etching rate and etching time. The relation between the etching time, track parameters (depth, radius) and D for different alpha particles energy and etching conditions were studied. A relation describing D as a function of track size is proposed.