Characterisation of proton irradiated CR-39 detector using positron annihilation lifetime spectroscopy

The damaged produced by proton beam slowed down in CR-39 polymer results in highest degree of disorder with change of free volume proprieties. Positron annihilation lifetime spectroscopy (PALS) is nowadays well recognized as powerful tool of microstructure investigations. PALS is used in order to get more information at an atomic scale of modifications induced by irradiation of polymers particularly the variation of free volume in the irradiated region. In this paper, the mean free volume hole radii and average free volume of the micro-voids in CR-39 polymer irradiated with 200 MeV therapy proton beam at different positions in spread out Bragg Peak region (SOBP) at Ithemba proton therapy facility have been determined using PALS. © 2006 Elsevier Ltd. All rights reserved.     

Microstructure of polycarbonate seen by positrons as an in-situ probe

Positron Annihilation Lifetime Spectroscopy (PALS) is used to probe the micro-structural changes in the polymer polycarbonate in terms of the changes in free volume hole size and their content as a function of temperature. The measured spectra are best fitted to three lifetime component analysis. The average hole size in the amorphous regions is determined from the measured Ortho Positronium (O-Ps) lifetime ₃ by following the treatment of Nakanishi et al. On the other hand, information about defects in the crystalline regions is revealed by trapped positrons lifetime ₂. In this polymer the average hole radius varies from 2.71 Å to 2.77 Å. The present study indicates that this polymer has a glass transition temperature of 152°C. Further, we have calculated the trapping rates in the ordered and disordered regions of the polymer based on Goldanskii's kinetic equations and an attempt is made for the first time to estimate the activation energy in the amorphous and crystalline regions separately.     

The investigation of electrochemical properties and ionic motion of functionalized copolymer electrolytes based on polysiloxane

The effect of EO side chain functionalization on the transport and electrochemical properties of polysiloxane electrolytes has been examined in this report. First, a study of the electrochemical stability of the electrolytes by linear sweep voltammetry shows that the polymer electrolytes have a negligible effect on the electrolyte stability windows. In addition, the parameters of cation mobility in polysiloxane electrolytes, such as ionic transference numbers and diffusion coefficients, were increased by increasing the lengths of the EO side chain. However, cation mobility in polymer structures is quite different compared to liquid-based systems and is probably suppressed, resulting in their polymer structure. Therefore, Positron Annihilation Lifetime Spectroscopy (PALS) was used to study the relationship between orthopositronium (o-Ps) lifetime, free volume radius, free volume of micro voids and EO side chain affection at different temperatures. Finally, a battery application with LiCoO₂ and LiFePO₄/polymer electrolyte/lithium metal electrode was monitored for its potential use in the future.     

SmFeAsO材料的正电子寿命研究

首次用正电子湮灭寿命谱仪（PALS）测量SmFeAsO多晶样品常温下的寿命谱,得到两个寿命成分1516 ps和2903 ps,根据捕获模型得到正电子在SmFeAsO中湮灭的体寿命为1870 ps,与理论计算（广义梯度近似）得到的SmFeAsO单晶中的正电子体寿命173 ps符合较好.基于中性原子叠加模型-有限差分方法(SNA-FD)的理论计算得到正电子与单晶SmFeAsO中各个原子价电子的总湮灭率是其与各个原子核心内层电子总湮灭率的106倍,正电子与Fe,As,Sm,O原子的电子湮灭的概率之比是1∶13∶12∶1. 关键词： 高温超导 正电子寿命     

Positron annihilation spectroscopy in tomorrow's material defect studies

Positron Annihilation Spectroscopy (PAS), sometimes refered to as Positron Annihilation Lifetime Spectroscopy (PALS), are non-destructive techniques commonly used for defects and voids study in materials. It provides a handy tool for in-depth profiling down to few microns, and in determining open volume defects like dislocation, agglomerates, and vacancies at ppm concentration. PAS with the aid of Doppler broadening has certainly opened a new gateway in the spectroscopy of solid state physics, metals, RO systems, and semiconductors. Since it is an antiparticle of the electron it gives better information on the electron density in the material of interest. The lifetime of a positron is a complex function of electron density present at the annihilation site. To add beauty, in principle PAS gives the type and concentration of the defect independently by a single measurement. This article presents PAS based on the most relevant, most iconic, and most recent references.     

Investigation of neutron emission from relativistic heavy ion interactions by nuclear tracks

Fast neutrons produced in 44 and 22 GeV ¹²C+Cu interactions have been recorded and analysed with a CR-39 detector stack. The irradiation of the CR-39 stack to fast neutrons was carried out at the accelerator Synchrophasotron, Joint Institute for Nuclear Research, Dubna, Russia. Areal and volume densities of tracks induced by fast neutrons in the CR-39 at different positions and for different etching time have been measured. The neutron production ratio of 44 GeV to 22 GeV ¹²C+Cu interactions has been obtained, which is 2.17 ± 0.30 by areal track density, or 2. 12±0.33 by step etch technique, or 2.03±0.34 by volume track density measurement. These results confirm that the production rate at 44 GeV ¹²C+Cu interactions is more than theoretical estimation.     

Detection of hydrogen in neutron-irradiated nickel using positron lifetime spectroscopy

Hydrogen in nano-voids in neutron-irradiated nickel has been detected using positron annihilation lifetime spectroscopy (PALS). As positron lifetime is greatly affected by nano-voids bound with hydrogen, special attention was paid to the analysis. The positron lifetime of neutron-irradiated nickel at higher irradiation doses increased with the dose, which is an indicator for vacancy cluster (nano-void) formation in the lattice. The introduction of hydrogen in well-annealed nickel by electrical charging also resulted in an increase in positron lifetime due to vacancy formation. In neutron-irradiated nickel specimens, hydrogen charging shortened the positron lifetime from 456 to 334 ps (irradiation dose: 3 × 10^?3 dpa). Isochronal annealing behaviour of hydrogen-charged nickel and neutron-irradiated nickel was also studied. Positron trapping rate was calculated using a simple trapping model. Thermal desorption spectroscopy was used for the investigation of hydrogen behaviour in non-irradiated hydrogen-charged nickel.     

Effect of iodine sorption on the free volume of polycarbonate

 The effect of iodine sorption on the free volume of polycarbonate is investigated by Positron Annihilation Lifetime method. The observed results are interpreted in terms of the Charge Transfer Complex formation and precipitation of iodine at the initial and final stages of sorption, respectively. At higher levels of sorption, changes in the second lifetime and its intensity seem to suggest a conformational transformation, probably due to the net change in the amorphous-crystalline boundary regions of the polymer matrix. The free volume cavities have been predominantly occupied by I^- ₃ species and the diffusion process obeys Fick’s law. An exponential type correlation has been observed between fractional free volume and the diffusion coefficient. Received: 13 June 1996/Accepted: 20 September 1996     

60Co的γ辐照对SB的自由体积和微结构的影响的PALS和FT-IR的研究

利用正电子湮没技术和傅里叶红外分析研究手段，基于Eldrup的自由体积孔经典模型，分别研究了⁶⁰Co的γ辐照剂量对聚苯乙烯-丁二烯二嵌段共聚物(SB)的自由体积和微结构变化的影响，并关联两种测试结果，确定了⁶⁰Co的γ辐照对SB的辐照交联和降解模型.而后用热重分析(TGA)研究了辐照前后的SB的热稳定，给出了自由体积参数变化与热稳定的关联. 关键词： 正电子湮没技术 正电子素 嵌段共聚物 γ辐射     

三嵌段共聚物SEBS中自由体积行为的温度及e+辐照时间依赖性的研究

利用正电子湮没寿命谱实验手段研究了²²Na放射源的e⁺自辐射对三 嵌段共聚物SEBS的正电子湮没参数的影响，而后结合Eldrup的经典模型，研究了SEBS的自由体积孔尺寸和自由体积分数随着温度的变化关系，给出了自由体积分数在T_g以上和在Tg以下各自区域内分别与温度呈线性关系，最后结合Williams-Landel-Ferry(WLF)自由体积理论和Eldrup的经典模型讨论了热膨胀系数和自由体积分数中的A常数. 关键词： 正电子湮没技术 嵌段共聚物 自辐射 热膨胀     

Study of optical band gap, carbonaceous clusters and structuring in CR-39 and PET polymers irradiated by 100 MeV O ions

Commercially purchased CR-39 and PET polymers were irradiated by 100 MeV O⁷⁺ ions of varying fluences, ranging from 1×10¹¹ to 1×10¹³ ions/cm². The effects of swift heavy ions (SHI) on the structural, optical and chemical properties of CR-39 and PET polymers were studied using X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The XRD patterns of CR-39 show that the intensity of the peak decreases with increasing ion fluence, which indicates that the semicrystalline structure of polymer changes to amorphous with increasing fluences. The XRD patterns of PET show a slight increase in the intensity of the peaks, indicating an increase in the crystallinity. The UV-visible spectra show the shift in the absorbance edge towards the higher wavelength, indicating the change in band gap. Band gap in PET and CR-39 found to be decrease from 3.87 to 2.91 and 5.3-3.5 eV, respectively. The cluster size also shows a variation in the carbon atoms per cluster that varies from 42 to 96 in CR-39 and from 78 to 139 in PET. The FTIR spectra show an overall reduction in intensity of the typical bands, indicating the degradation of polymers after irradiation.     

Conduction in ionic organic plastic crystals: The role of defects

This paper describes the relationship between the ionic conduction and the characteristics of defects in plastic crystalline phases of N,N-dimethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P₁₁TFSA). Positron annihilation lifetime spectroscopy (PALS) shows that the phase III to phase II transition involves the generation and expansion of vacancies, which is confirmed by measurement of volumetric expansion. The vacancies expand to match the cation size in phase II and this gives rise to an increase in the conductivity. The relationship between the vacancy volume and the conductivity obeys a Cohen–Turnbull free volume conduction model. The critical volume matches the volume of a cation–anion pair in phase III, which indicates a Schottky mechanism. The critical volume shows a greater value in phase II, which is probably indicative of a pipe diffusion mechanism.     

FT-IR spectroscopy of carbon dioxide in CR-39 and SR-90 track detectors irradiated with ions and gamma-rays at different energies and fluences

Two types of polymeric track detectors CR-39 and SR-90 were irradiated with protons, alpha particles, heavy ions and gamma-rays at different energies and fluences. After irradiation these detectors were analyzed with an FT-IR spectrometer of Jasco type 5300 in transmission and ATR modes. We have found that CO₂ is produced not only by irradiation but also by polymerization. The amount of CO₂ in the detector material is closely related to the latent track formation.     

A study of the effect of gamma and laser irradiation on the thermal,optical and structural properties of CR-39 nuclear track detector

A comparative study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of the CR-39 diglycol carbonate solid state nuclear track detector has been carried out. Samples from CR-39 polymer were classified into two main groups: the first group was irradiated by gamma rays with doses at levels between 20 and 300 kGy, whereas the second group was exposed to infrared laser radiation with energy fluences at levels between 0.71 and 8.53 J/cm². Non-isothermal studies were carried out using thermogravimetry, differential thermogravimetry and differential thermal analysis to obtain activation energy of decomposition and transition temperatures for the non-irradiated and all irradiated CR-39 samples. In addition, optical and structural property studies were performed on non-irradiated and irradiated CR-39 samples using refractive index and X-ray diffraction measurements. Variation in the onset temperature of decomposition T _o, activation energy of decomposition E _a, melting temperature T _m, refractive index n and the mass fraction of the amorphous phase after gamma and laser irradiation were studied.

It was found that many changes in the thermal, optical and structural properties of the CR-39 polymer could be produced by gamma irradiation via degradation and cross-linking mechanisms. Also, the gamma dose has an advantage of increasing the correlation between thermal stability of the CR-39 polymer and bond formation created by the ionizing effect of gamma radiation. On the other hand, higher laser-energy fluences in the range 4.27–8.53 J/cm² decrease the melting temperature of the CR-39 polymer and this is most suitable for applications requiring molding of the polymer at lower temperatures.     

Application of positron beams to the study of positronium-forming solids

Doppler broadening of annihilation radiation (DBAR) and positron annihilation lifetime spectroscopy (PALS) have been successfully applied to the study of positronium (Ps)—forming amorphous solids such as polymers and silicon oxide in the bulk. Implementing depth selectivity to DBAR and PALS by combining them with variable-energy positron beams considerably broadens their applicability. Variation of incident positron energy over a wide range enables depth-profiling, whereas tuning of the beam energy enables the studies of surfaces, interfaces and thin films. In this paper, we discuss fundamentals and applications of energy variable DBAR and PALS for Ps—forming polymers and silicon oxide.     

高聚物正电子谱学的研究进展

简要介绍了近年来正电子谱学在聚合物微结构研究中的主要应用及进展,大量实验事实表明,正电子谱学是表征高聚物微结构的极灵敏方法。     

Ion beam modification of surface properties of CR-39

The effects of ion-beam bombardment on the physical and chemical properties of poly(allyl diglycol carbonate) (CR-39) polymer have been investigated. CR-39 samples were bombarded with 320 keV Ar and 130 keV He ions at fluences ranging from 1 × 10¹³ to 2 × 10¹⁶ ions/cm². The nature and extent of radiation damage induced were studied by UV–VIS spectrometry, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, as well as Vickers' hardness measurements. In addition, the effect of ion fluence on the wetting properties of ion-beam bombarded CR-39 polymer was determined by measuring the contact angle for distilled water. UV–VIS spectra of bombarded samples reveal that the optical band gap decreases with increasing ion fluence for both Ar and He ions. In the FTIR spectra, changes in the intensity of the bands on irradiation relative to pristine samples occurred with the appearance of new bands. XRD analyses showed that the degree of ordering of the CR-39 polymer is dependent on the ion fluence. Changes of surface layer composition and an increase in the number of carbonaceous clusters produced important change in the energy gap and the surface wettability. The surface hardness increased from 10.54 MPa for pristine samples to 28.98 and 23.35 MPa for samples bombarded with Ar and He ions at the highest fluence, respectively.     

Ionic conductivity of PVdF-co-HFP/LiClO4 in terms of free volume defects probed by positron annihilation lifetime spectroscopy

ABSTRACT

Polymers based on ionic conducting materials have important interest because of their potential applications in polymer electrolytes and membranes for fuel cell application. PVdF-co-HFP poly(viniliden-co-hexafluoropropylene) was chosen as a polymer matrix because of its high ionic conductivity and better mechanical properties. Polymer matrix composites were prepared with various amounts of LiClO₄ salt by a solution casting method. The sample-ionic conductivity measurements were recorded by AC impedance analyzer at different frequencies from 0.1?Hz to 20?MHz and at different temperatures from 273 to 373?K.

The changes of nanoscopic free volume and free volume fraction in these materials were investigated in terms of temperature from 273 to 373?K using Positron Annihilation Lifetime Spectroscopy (PALS) and Simha-Somcynsky (SS) Hole Theory. The free volume had a bump at about 3% in weight percentage of the salt and there is a slight increase after 10%. The effects of weight percentages of LiClO₄ and temperature were investigated. The mechanism of the ac ionic conductivity was presented in terms of the free volume models, however thermo-occupancy function justifies the best accurate representation of the data.     

Degradation Studies of Polyolefins Incorporating Transparent Nanoparticulate Zinc Oxide UV Stabilizers

Coated and dispersed nanoparticulate zinc oxide is shown to improve ultra violet (UV) stability of polypropylene and high-density polyethylene without changing its characteristic absorption spectrum in the visible region (400–800-nm). The performance of these nanoparticulate UV stabilizers is compared to conventional hindered amine light stabilizers (HALS). QUV accelerated weathering is used to simulate long-term exposure. Positron annihilation lifetime spectroscopy (PALS) is used to provide an indication of physical and chemical changes due to accelerated weathering and is shown to have potential for detecting changes well before other techniques. Visual observation, optical microscopy, carbonyl index, yellowness index and PALS indicate that nanoparticulate zinc oxide gives superior resistance to UV degradation compared to organic HALS at appropriate loading levels.     

Correlation of soft magnetic properties with free volume and medium range ordering in metallic glasses probed by fluctuation microscopy and positron annihilation technique

Amorphous ribbons of different thicknesses of Co_64.5Fe_3.5Si₁₆B₁₄Ni₂ alloy were synthesized using the melt spinning technique by varying wheel speed. The effect of cooling rate on the ribbon thickness and their soft magnetic properties have been studied. The amorphous structure has been characterized in terms of structural free volume and medium range order (MRO) by positron annihilation spectroscopy and fluctuation electron microscopy techniques. Positron lifetime spectra of amorphous samples showed two lifetime components. The first component was found to be correlated with MRO whereas, the second lifetime component was found to be associated with nanovoid type of defects, and the second component was strongly dependent on processing conditions. It could be established that the coercivity of the amorphous samples produced by the rapid solidification technique mainly depends on the defects formed during processing rather than change induced in MRO.