The thermoluminescence response of Ge-doped optical fibre subjected to photon irradiation

A radiation dosimeter based on Ge-doped silica fibre is described. Parameters concerning thermoluminescence (TL) induced by ⁶⁰Co irradiation are investigated, including activation energies, frequency factors, and reproducibility with dose and fading. It is concluded that Ge-doped silica fibres provide a good basis for medical radiation dosimetry at therapy levels. In particular, doses are reproducible to within 3%, the fibres are reusable and show linearity of dose versus TL output over the approximate range of dose 1 Gy to in excess of 100 Gy. At room temperatures, fading within the first 30 d following irradiation has been found to be of the order of 7%.     

Three-dimensional polymer gel dosimetry: basic physical properties of the dosimeter

This study concentrated on assessment of the basic physical properties of a polymer gel dosimeter evaluated by NMR. For this, BANG-2 type polymer gel was prepared. The dosimeters were irradiated by ⁶⁰Co gamma photons and by 4, 6 and 18 MV X-ray photons for doses in the range 0–50 Gy. The multi-echo CPMG sequence was used for the evaluation of T₂-relaxation times in the irradiated gel dosimeters. Dependence of 1/T₂ in terms of the following factors was studied: absorbed dose, energy of applied radiation, temperature during NMR evaluation, time between irradiation and NMR evaluation and strength of the magnetic field. An exponential dependence of the 1/T₂ response on absorbed dose in the range 0–50 Gy was observed, while in the range 0–10 Gy the data could be fitted by a linear function. This paper also describes the dependence of 1/T₂ response on: radiation energy, strength of magnetic field and time from irradiation of the dosimeters to NMR evaluation. Increase of gel dosimeter 1/T₂ response with the decrease of the temperature during NMR evaluation has been qantitatively described. The polymer gel dosimetry system used in this study proved that it is a reliable system for three-dimensional dose distribution measurement.     

Laser-induced breakdown spectroscopy of γ-Fe2O3 nanoparticles in a biocompatible alginate matrix

An intensive multi-disciplinary research effort is underway at Wayne State University to synthesize and characterize magnetic nanoparticles in a biocompatible matrix for biomedical applications. The particular system being studied consists of 3–10 nm γ-Fe₂O₃ nanoparticles in an alginate matrix, which is being studied for applications in targeted drug delivery, as a magnetic-resonance imaging (MRI) contrast agent, and for hyperthermic treatments of malignant tumors. In the present work we report on our efforts to determine if laser-induced breakdown spectroscopy (LIBS) can offer a more accurate and substantially faster determination of iron content in such nanoparticle-containing materials than competing technologies such as inductively-coupled plasma (ICP). Standardized samples of -Fe₂O₃ nanoparticles (5–25 nm diameter) and silver micropowder (2–3.5 μm diameter) were created with thirteen precisely known concentrations and pressed hydraulically to create solid “pellets” for LIBS analysis. The ratio of the intensity of an Fe(I) emission line at 371.994 nm to that of an Ag(I) line at 328.069 nm was used to create a calibration curve exhibiting an exponential dependence on Fe mass fraction. Using this curve, an “unknown” γ-Fe₂O₃/alginate/silver pellet was tested, leading to a measurement of the mass fraction of Fe in the nanoparticle/alginate matrix of 51 ± 3 wt.%, which is in very good agreement with expectations and previous determinations of its iron concentration.     

Effects of (60)Co gamma radiation on thylakoid membrane functions in Anacystis nidulans

In photosynthetic organisms oxidative stress is known to result in photoinactivation of photosynthetic machinery. We investigated effects of ⁶⁰Co γ radiation, which generates oxidative stress, on thylakoid structure and function in cyanobacteria. Cells of unicellular, non-nitrogen fixing cyanobacterium Anacystis nidulans (Synechococcus sp.) showed D₁₀ value of 257 Gy of ⁶⁰Co γ radiation. When measured immediately after exposure, cells irradiated with 1500 Gy (lethal dose) of ⁶⁰Co γ radiation did not show any differences in photosynthetic functions such as CO₂ fixation, O₂ evolution and partial reactions of photosynthetic electron transport in comparison to unirradiated cells. Incubation of irradiated cells for 24 h in light or dark resulted in decline in photosynthesis. The decline in photosynthesis was higher in the cells incubated in light as compared to the cells incubated in dark. Among the partial reactions of electron transport, only PSII activity declined drastically after incubation of irradiated samples. This was also supported by the analysis of membrane functions using thermoluminescence. Exposure of cyanobacteria to high doses of ⁶⁰Co γ radiation did not affect the thylakoid membrane ultrastructure immediately after exposure as shown by electron microscopy. The level of reactive oxygen species (ROS) in irradiated cells was 20 times higher as compared to control. In irradiated cells de novo protein synthesis was reduced considerably immediately after irradiation. Treatment of cells with tetracycline also affected photosynthesis as in irradiated cells. The results showed that photoinhibition of photosynthetic apparatus after incubation of irradiated cells was probably augmented due to reduced protein synthesis. Active photosynthesis is known to require uninterrupted replenishment of some of the proteins involved in electron transport chain. The defective thylakoid membrane biogenesis may be leading to photosynthetic decline post-irradiation.     

The use of ESR spectroscopy for the investigation of dosimetric properties of egg shells

Electron spin resonance (ESR) spectroscopy was used to investigate the dosimetric properties of chicken egg shells. The ESR spectra of the irradiated egg shell were found to have an asymmetric absorption characterized by a major resonance at g=2.0019 and a minor resonance at g_||=1.9980. The study was carried out on g=2.0019 signal because of the accuracy of measurements and the possibility of using it as ESR dosimeter. The activation energy (E), frequency factor (k₀) and mean-life (τ) were calculated to be 1.50±0.10 eV, 2×10¹³ s⁻¹ and (4.4±0.4)×10⁴ year respectively. Dose–response was investigated between dose ranges of 1 Gy and 10 kGy for ⁶⁰Co γ-rays. Dose–response was found to be appropriate for dosimetry in the range 3 Gy to 10 kGy. The lower limit of observable doses for egg shell sample was about 3 Gy. The other ESR dosimetric parameters of egg shell samples, fading characteristic, light effect, dose-rate dependence and energy dependence, have also been studied in detail. Apart from its non-tissue equivalence, egg shell has very good dosimetric properties with insignificant fading, light independence, linearity in dose–response (3 Gy–10 kGy), dose-rate independence and independence from energy above 500 keV. It suggests that egg shell may be used as a retrospective γ radiation dosimetry after nuclear accidents or other short accidental radiation events.     

Radiation polymerization of thermo-sensitive poly (N-vinylcaprolactam)

Temperature-sensitive poly (N-vinylcaprolactam) both in water-soluble state and in gel was prepared by γ-radiation polymerization. The effects of radiation dose, radiation dose rate and monomer concentration on polymerization and the low critical solution temperature characteristics of the polymer were studied. The results show that the polymer prepared within certain radiation dose (beyond 2 kGy) and dose rate range (2–14 Gy/min) has good temperature sensitivity and uniformity.     

Threonine-FX dosimeter for food irradiation

A detailed study for the spectrophotometric readout method for L-threonine powder, [CH₃CH(OH)CH(NH₂)COOH], was done. In this method, 400 mg unirradiated/irradiated L-threonine powder was dissolved in 10 ml of a solution which contains 3×10⁻⁴ mol dm⁻³ ferrous ammonium sulphate and 1.7×10⁻⁴ mol dm⁻³ xylenol orange (XO) in aerated aqueous 0.17 mol dm⁻³ sulphuric acid (FX). The peroxy radicals produced from irradiated threonine oxidize ferrous ions and XO forms a complex with ferric ions as well as controls the chain length of ferrous ion oxidation. The plot of absorbance at 556 nm against dose is linear in the dose range 20–400 Gy and doses down to about 1 Gy can be measured using 10-cm path cells. Response of the dosimeter is independent of irradiation temperature above 20. A dose of 50 Gy–10 kGy can be measured dissolving 50 mg threonine powder in 10 ml of a solution which contains 3×10⁻⁴ mol dm⁻³ ferrous ammonium sulphate and 1.3×10⁻⁴ mol dm⁻³ XO in aerated aqueous 0.06 mol dm⁻³ sulphuric acid (FX). The plot of absorbance at 552 nm against dose is non-linear. However dosimeter shows linear dose response up to 1000 Gy. Irradiated threonine powder is stable for about 3 months. The reproducibility of the method is better than ±2%. This dosimeter is very useful as transfer dosimeter for food irradiation programme.     

Effects of gamma radiation on codling moth, Cydia pomonella (L.), eggs

The radiosensitivity of codling moth, Cydia pomonella (L.), eggs in different stages of development was studied. Eggs ranging in age from 1–24 to 97–120 h were exposed, at 24 h intervals, to gamma radiation doses ranging from 10 to 350 Gy. The effects of gamma radiation on egg hatch, pupation and adult emergence was examined. Results showed that the radiosensitivity of codling moth eggs decreased with increasing age. Egg hatch in 1–24 h old eggs was significantly affected at 20 Gy dose and at 60 Gy dose, egg hatch decreased to about 1%. At the age of 25–48 h, however, egg hatch at 60 Gy dose was about 10%, and egg sensitivity to gamma irradiation decreased significantly in the 49–72 h age group; 60 Gy dose had no significant effect on egg hatch. Eggs irradiated few hours before hatch (at the blackhead stage), were the most resistant ones; 100 Gy had no significant effect on egg hatch and at 350 Gy dose over 56% of the eggs hatched. When adult emergence was used as a criterion for measuring effectiveness, however, the effect of gamma radiation was very sever. A dose of 60 Gy completely prevented adult emergence and at 100 Gy dose all resulted larvae died before pupation.     

FT-IR and Raman spectroscopic study of di-urea cross-linked poly(oxyethylene)/siloxane ormolytes doped with Zn ions

The interactions occurring in di-urea (NHC(O)NH) cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils) doped with zinc triflate (Zn(CF₃SO₃)₂) were investigated by Fourier Transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies. Bonding of the Zn²⁺ ions to the urea carbonyl oxygen atoms occurs in the entire range of compositions studied (∞ > n ≥ 1, where n, salt content, is the molar ratio of oxyethylene moieties per Zn²⁺ ion). At n > 20 the incorporation of the guest cations progressively reduces the number of free CO groups. At n = 20 the saturation of the urea cross-links is attained and the Zn²⁺ ions start to coordinate to the POE chains giving rise to the formation of a crystalline POE/Zn(CF₃SO₃)₂ complex. The latter process occurs at the expense of the destruction of the hydrogen-bonded POE/urea structures of the host di-ureasil structure. New hydrogen-bonded associations, more ordered than the urea–urea aggregates present in the non-doped matrix and including Zn²⁺OC coordination, emerge in parallel. “Free” and weakly coordinated CF₃SO₃⁻ ions, present in all the xerogels studied, appear to be the main charge carriers of the conductivity maximum of this family of ormolytes located at n = 60 at 30 °C. In materials with n ≤ 20 contact ion pairs, “cross-link separated” ions pairs and higher ionic aggregates appear. The data reported demonstrate that the behaviour of the di-ureasils doped with triflate salts depends on the type of cation.     

Comparison of γ-radiation and electron beam irradiation effects on gelatin

Gelatin is a heterogeneous mixture of water-soluble proteins of high average molecular weight derived by hydrolytic action from collagen, a protein of mammal external protective tissues. There are many characteristics of a material that can indicate its quality or performance in its intended use. The knowledge of a material's rheological characteristics is valuable to predict its pourability, its performance in a dipping or coating operation or the ease with which it may be handled, processed or used. In this work bovine powder gelatin was submitted to γ-radiation from a ⁶⁰Co source, dose rate about 7 kGy/h and to electron beam irradiation, dose rate about 11 kGy/s. The doses applied were 5, 10, 20 and 50 kGy. The radiation effects were measured following viscosity changes at 40°C of gelatin powder 10% aqueous solutions. The relationship between the decrease in viscosity of gelatin solutions and radiation dose presented close comparable values for both irradiation processes.     

Accelerate ageing of PZT-type ceramics

Accelerate ageing of lead zirconate–titanate ferroceramics (PZT) by fast neutron irradiation is investigated. The ferroelectric behavior of Pb_1−wM_w(Zr,Ti)O₃, where w < 0.5 wt%, M = Li, Nb, Cr, Bi, Mn, Sb, La for Zr/Ti ratio = 51.5/48.5, prepared by solid state reaction, is strongly affected by fast neutron irradiation at Φ_i = (10¹³ ÷ 10¹⁸) n/cm² integrated fluxes. Structural investigations (XRD and SEM) reveal modifications of the microstructure, porosity and elementary cell parameters. High irradiation levels induce tetragonal-cubic at the same time with a ferro–paraelectric transition. The micrographs show the evolution of 90° and 180° walls as well as herringbone structure typical for tetragonal distortions with irradiation level. A relation between macroscopic characteristics (piezoelectric and dielectric) and microscopic properties (crystallographic parameters, porous structure and grain morphology) as function of irradiation doses can be established using a model based on microstructural parameters. These results offer opportunities to understand the fundamentals of radiation effects upon piezoelectric ceramics.     

Electron beam treatment parameters for control of stored product insects

The fluidized bed process (EBFB) has been evaluated for the disinfestation of cereal grains. The various life stages from egg to adult have been studied on the 225 kV pilot as a function of surface dose. Three of the most common pests were selected: the rice weevil (S. oryzae), the lesser grain borer (R. dominica) and the red flour beetle (T. castaneum). The major challenge to this process lies in those “protected” life-stages active deeply within the endosperm of the grain kernel. The rice weevil is such an internal feeder in which the larvae develop through several molts during several weeks before pupation and adult emergence. Product velocities up to 2000 m/min have been used for infested hard winter wheat at dose levels up to 1000 Gy. Detailed depth of penetration studies at three life stages of S. oryzae larvae were conducted at 225–700 kV and demonstrated effective mortality at 400 kV×200 Gy. Mortality data are also presented for the radiation labile eggs of these insects as well as the (sterile) adults, which typically lived for several weeks before death. These results are compared with earlier ⁶⁰Co gamma-ray studies on these same insects. Based upon these studies, the effectiveness of the fluidized bed process employing self-shielded electron beam equipment for insect control in wheat/rice at sub-kilogray dose levels has been demonstrated.     

Preparation of the hydrocarbon-soluble trifluoro complex LTiF3 with a β-diketiminato ligand

The β-diketiminato fluoride complex (LTiF₃) (1) (L = HC(CMeN(2,6-iPr₂C₆H₃))₂, “NacNac”) has been obtained using two synthetic routes, interaction of TiF₄ and NacNacK·2THF in toluene and interaction of LTiCl₃ and 3 equiv. of Me₃SnF in toluene. The trifluoro complex (LTiF₃) (1) is soluble in the non-polar solvents toluene and hexane and moderately active in polymerization of ethylene; the activity is higher than that of LTiMe₃ and comparable with that of the oxo-bridged complexes LTiCl(μ-O)₂TiClL and LTiMe(μ-O)₂TiMeL·toluene. Compound 1 was characterized by single crystal X-ray structural analysis, elemental analysis, NMR spectroscopy, and mass spectrometry. Complex 1 in the solid state is a centrosymmetric dimer containing two LTiF₂ moieties connected by two bridging fluorines, whereas C₆D₆ and CD₃CN solutions of 1 contain the monomeric complex at room temperature.     

Concerning the crystal structure of BrF3·AuF3

Crystals of the adduct, BrF₃·AuF₃, are monoclinic, with: a=5.356(4) Å, b=5.766(4) Å, c=8.649(3) Å, β=101.39(4)°, V=261.8(5) Å³, z=2, D_c=4.96 g/cm³. An ordered structure in P2₁ was found, but is of low precision (R₁=0.082) because of crystal deformation. The structure has planar BrF₄ units sharing F ligands cis with planar AuF₄ groups, each AuF₄ being similarly linked to two BrF₄. This generates a ribbon, creased at the bridging F along y, the gold on one side of the crease, the bromine on the other. Such ribbons are stacked parallel along y, with nearest neighbors related by twofold screw axes. This sandwiches each AuF₄ strip of a ribbon symmetrically between like strips. These contacts between the Au-strips bring up, to each Au-atom, two “non-bridging Au–F ligands” of each of the two neighboring strips, to give eight coordination in F. The bromine side of the creased ribbon is unsymmetrically sandwiched between a screw-axis related relative, and the edge of a Au-containing strip oriented almost perpendicular to it. This brings two non-bridging F of the nearest-strip BrF₄ and two non-bridging F of the AuF₄ strip into the secondary cordination sphere of the Br atom. Raman spectra of the BrF₃·AuF₃, molecular BrF₃, and polymeric AuF₃ suggest that the Br–F and Au–F stretching vibrations of BrF₃·AuF₃ are shifted slightly from those of the parent BrF₃ and AuF₃, and indicate some BrF₂⁺AuF₄⁻ character.     

Advancements in internationally accepted standards for radiation processing

Three subcommittees of the American Society for Testing and Materials (ASTM) are developing standards on various aspects of radiation processing. Subcommittee E10.01 “Dosimetry for Radiation Processing” has published 9 standards on how to select and calibrate dosimeters, where to put them, how many to use, and how to use individual types of dosimeter systems. The group is also developing standards on how to use gamma, electron beam, and x-ray facilities for radiation processing, and a standard on how to treat dose uncertainties. Efforts are underway to promote inclusion of these standards into procedures now being developed by government agencies and by international groups such as the United Nations' International Consultative Group on Food Irradiation (ICGFI) in order to harmonize regulations and help avoid trade barriers.

Subcommittee F10.10 “Food Processing and Packaging” has completed standards on good irradiation practices for meat and poultry and for fresh fruits, and is developing similar standards for the irradiation of seafood and spices. These food-related standards are based on practices previously published by ICGFI.

Subcommittee E10.07 on “Radiation Dosimetry for Radiation Effects on Materials and Devices” principally develops standards for determining doses for radiation hardness testing of electronics. Some, including their standards on the Fricke and TLD dosimetry systems are equally useful in other radiation processing applications.     

Effects of gamma irradiation on the shoot length of Cicer seeds

The effects of radiation on the shoot and root lengths of germinated seedling of irradiated seeds of Cicer species, i.e. three kabuli types and four desi types of cultivated chickpea (Cicer arietinum Ladiz.) and 2 annual wild types (C. reticulatum Ladiz. and C. bijugum K.H. Rech.) were investigated. The seeds were irradiated with a ⁶⁰Co gamma source using 0, 200, 300 and 400 Gy doses at 1.66 kGy h⁻¹. At 200 Gy minor effects could be observed, but at 400 Gy an obvious depression of shoot length was observed. The kabuli types were more affected than the desi ones. The critical dose that prevented the shoot and root elongation varied among species and also ranged from genotypes to genotype within species.     

New Structure Formation on γ-irradiation of Poly(chlorotrifluoroethylene)

The radiation chemistry of PCTFE at different temperatures has been studied. The polymer was irradiated under vacuum to absorbed doses of up to 1500 kGy. Three irradiation temperatures were chosen. These included ambient temperature, a temperature well above the T_g and a temperature above the crystalline melting temperature. These were 298, 423 and 493 K, respectively. The formation of new structures was identified by solid-state FTIR and ¹⁹F NMR. No branching was observed below the melting temperature, but branches were observed above the melting temperature. G-values for chain-end formation were 1.5 and 2.4 at room temperature and 423 K, respectively and the G-value for the formation of double bonds was found to be <0.1. For the irradiations at 493 K, the G-values for the formation of chain ends, double bonds and branching points were 3.6, 0.2 and 0.5, respectively. The presence of long-chain branches within the polymer structure could not be proven for radiolysis at 493 K, but scission predominates and network formation does not occur upon irradiation. DSC studies of the polymers irradiated at ambient temperature were consistent with chain scission leading to an increase in the percentage crystallinity, as observed for other fluoropolymers.     

A selective optical sensor for picric acid assay based on photopolymerization of 3-(N-methacryloyl) amino-9-ethylcarbazole

A novel optical sensor based on covalent immobilization for picric acid assay has been described. To improve the stability of the sensor, a terminal double bond was attached to the fluorescent compound, 3-amino-9-ethylcarbazole (AEC), via methacryloyl chloride. The resultant compound, 3-(N-methacryloyl) amino-9-ethylcarbazole (MAEC) was copolymerized with 2-hydroxypropyl methacrylate on surface-modified quartz glass plates by UV irradiation. The resulting optical sensor (optode membrane) was used to determine picric acid based on fluorescence quenching. It shows a linear response toward picric acid in the concentration range of 9.33 × 10⁻⁸ to 9.33 × 10⁻⁵ mol l⁻¹, with rapid response, high stability and good selectivity to picric acid.     

Radiochromic gel dosemeter for three-dimensional dosimetry

A gel dosemeter in which ionising radiation causes a colour change was produced by modifying an existing Fricke gel system. This allows a more convenient preparation procedure and gives a better quality dosimetric system for three-dimensional (3-D) dose measurements. The role of three active components of the Ferrous sulphate Xylenol orange Gelatin (FXG) gel dosemeter is quantified with special consideration of their effect on system sensitivity and stability. The optimal composition was found to be 0.5 mM ferrous sulphate, 0.1 mM xylenol orange and 25 mM sulphuric acid. The dose response is linear in the range 0.1–30 Gy. The FXG sensitivity, derived from the gradient of the dose response curve, was found to be ΔA=0.084 cm⁻¹ Gy⁻¹, where A is the optical absorption coefficient at a wavelength of 585 nm, with reproducibility and 24 h stability of better than 5%.     

Polymer evolution of a sulfonated polysulfone membrane as a function of ion beam irradiation fluence

Ion beam irradiation was used to modify the surface of a sulfonated polysulfone water treatment membrane. A beam of 25 keV H⁺ ions with three irradiation fluences (1 × 10¹³ ions/cm², 5 × 10¹³ ions/cm², and 1 × 10¹⁴ ions/cm²) was used for membrane irradiation. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analyses were performed on the virgin and irradiated membranes in order to determine the changes to chemical structure incurred by ion beam irradiation. The results show that some of the sulphonic and CH bonds were broken and new CS bonds were formed after irradiation. Atomic force microscope (AFM) analyses show that membrane roughness decreased after irradiation. A significant increase in flux after ion beam irradiation was also observed, while the amount of cake accumulation on the membrane was decreased after ion beam irradiation. Hydrophobicity, pore size distribution and selectivity of the membrane were not affected by ion beam irradiation.