Measurements and calculations of absorbed dose in electron beam radiation processing

An electron beam current densimeter has been described and used for dose measurement in EB radiation processing. An improved bipartition model of electron transport is applied to calculate the reflection coefficients and energy deposition distributions produced by 0.2–3 MeV electrons in semi-infinite media of Al, C, MAR and nylon, and the energy deposition produced by 2 MeV electrons in the two-layer medium consisting of copper and polystyrene. In addition, the depth dose distribution of 300 keV electrons in Ti-air-nylon composite-layer has been evaluated. The calculation results are in good agreement with the measurement data.     

Calorimeters for absorbed dose standard of electron beam radiation processing

Graphite and water calorimeters which are intended to be used as standard dosimeters for radiation processing of electron beams are studied at NIM. The result of dose comparison between the two calorimeters is satisfactory. Moreover, the dose comparison between NIM calorimeters and NIM chemical liquid dosimeters is performed and the agreement is within 0.5%. Uncertainties in dose measurement with the two calorimeters are estimated.     

Electron beam irradiated textile cellulose fibres.: ESR studies and derivatisation with glycidyl methacrylate (GMA)

Powdered samples of cotton, flax and viscose from textile fibres were subjected to electron beam irradiation (20-400 KGy). ESR signals were observed after irradiation. The intensity of the signals depended on the administered dose and exhibited an exponential decay with time. The ESR spectra, whose pattern depended drastically on the crystallinity of the samples, indicated the simultaneous presence of at least three carbon-centred radical species. When the whole irradiated textile fibres were quenched in a solution of glycidyl methacrylate (GMA) a significant increase of the weight was observed, the increase being strongly dependent on the administered dose and on the time interval elapsed between irradiation and quenching. Spectroscopic characterisation evidenced that GMA acted as cellulose radicals scavenger on the unsubstituted carbon of the double bond and was covalently linked to the fibre through a new C-C bond while maintaining unaltered the ester and the epoxide groups, available for further derivatisations. Because irradiation of the whole textile fibres in the range 20-200 KGy does not result in significant degradation of the material, GMA quenching of fibres irradiated in this dose range may represent an attractive route to their functionalisation.     

Effects of physics change in Monte Carlo code on electron pencil beam dose distributions

Pencil beam algorithms used in computerized electron beam dose planning are usually described using the small angle multiple scattering theory. Alternatively, the pencil beams can be generated by Monte Carlo simulation of electron transport. In a previous work, the 4th version of the Electron Gamma Shower (EGS) Monte Carlo code was used to obtain dose distributions from monoenergetic electron pencil beam, with incident energy between 1 MeV and 50 MeV, interacting at the surface of a large cylindrical homogeneous water phantom. In 2000, a new version of this Monte Carlo code has been made available by the National Research Council of Canada (NRC), which includes various improvements in its electron-transport algorithms. In the present work, we were interested to see if the new physics in this version produces pencil beam dose distributions very different from those calculated with oldest one. The purpose of this study is to quantify as well as to understand these differences. We have compared a series of pencil beam dose distributions scored in cylindrical geometry, for electron energies between 1 MeV and 50 MeV calculated with two versions of the Electron Gamma Shower Monte Carlo Code. Data calculated and compared include isodose distributions, radial dose distributions and fractions of energy deposition. Our results for radial dose distributions show agreement within 10% between doses calculated by the two codes for voxels closer to the pencil beam central axis, while the differences are up to 30% for longer distances. For fractions of energy deposition, the results of the EGS4 are in good agreement (within 2%) with those calculated by EGSnrc at shallow depths for all energies, whereas a slightly worse agreement (15%) is observed at deeper distances. These differences may be mainly attributed to the different multiple scattering for electron transport adopted in these two codes and the inclusion of spin effect, which produces an increase of the effective range of electrons.     

Development of an up-flow irradiation device for electron beam wastewater treatment

Electron beam irradiation processing is an available technology to treat sludge, groundwater, surface water and industrial and municipal wastewater. The use of this technology into environmental areas has moved slowly because industry and government are always conservative in the adoption of new processes, especially when they can not observe the efficiency and cost effectiveness of a treatment in a full scale facility.

In this direction the hydraulic system where the water is presented to the electron beam governs the efficacy of this technology. The present work is based on the development of the irradiation device, an up-flow delivery system that alleviates the dependence of energy transfer to the stream with the beam accelerating voltage (penetration capability).

In this work a series of experiments were performed to establish the relationships between accelerating voltage ranging from 0.5 to 1.5 MeV, current, water flow and deposited dose in order to optimize the operating parameters and the selection of a cost-effective commercial electron beam.     

双吡啶盐/酞菁体系的光诱导电子转移的ESR研究

研究了五种金属酞菁化合物与一系列双吡啶高氨酸盐（PQ2+）之间在苯中的光诱导电子转移．对于酞菁／PQ2+／苯体系，在可见光辐照下，酞菁化合物的价带电子可被激发至导带，然后于界面发生电子转移使PQ2+盐变成离子基PQ+，给出较弱的ESR信号；当有表面活性剂氯代十四烷基吡啶和电子给体三乙醇胺存在时，可使PQ基的ESR信号显著增强5～6信以上．当有氧存在时，PQ+基信号迅速消失，给出较明显的超氧负离子基O2-的信号．氧能严重抑制电子转移的过程．     

Progress on standardization of electron beam dosimetry for radiation processing

The high dose standards and dissemination system of electron beams are being established at NIM. The graphite and/ or water calorimeters and liquid chemical dosimeter are to be accepted as standards. The transfer dosimeter selected are alanine/ESR dosimeter and radiochromic film (FWT - 60). Several kinds of radiochromic films, undyed cellulose triacetate, polyethylene and blue cellophane will be recommended as working dosimeter. A series of intercomparison studies are conducted between calorimeter and dichromate dosimeter. Agreement is found within 2%. Water calorimeters and dichromate dosimeters are used to make absolute dosimetric measurements of electron beams. These calibrated beams are then used to calibrate several types of dosimeters, such as alanine, radiochromic films, undyed and dyed polyethylene. Preliminary studies show that water calorimeter and dichromate dosimeter are reproducible and sufficiently accurate for electron beam calibration. The estimated overall uncertainty of the measurement is better than 5% at 95% confidence level.     

A mechanism for the electron beam lithography of solvent-soluble photosensitive polyimides

Solvent-soluble and intrinsically photosensitive polyimides were prepared, and their electron beam reaction was investigated. Negative tone patterns were formed by the electron beam irradiation of PI(BTDA/DEDPM) and PI(BEDA/DEDPM). The mechanism for the pattern formation of PI(BTDA/DEDPM) was determined from transient absorption measurements, changes in the molecular weights, and IR spectrum measurements to be crosslinking via hydrogen abstraction by the triplet excited state benzophenone moiety. For the case of PI(BEDA/DEDPM), the pattern was formed by insolubilization due to chemical change in the polymer. These reactions are found to be so inhomogeneous that insolubilization of the polymer occurs at an early stage of gelation.     

Modification of fluoropolymers by means of electron beam irradiation

High molecular weight polytetrafluoroethylene (PTFE) is transformed to free-flowing micropowder by treatment with electron beams. In case of irradiation in presence of air carboxylic acid fluoride groups are incorporated which rapidly hydrolyze to carboxylic groups in the surface-near regions due to atmospheric humidity. These polar groups reduce the hydrophobic and oleophobic properties so much that homogeneous compounding with other materials becomes possible. In addition to PTFE, copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) and perfluoropropylvinylether (PFA) were modified. In case of identical irradiation conditions, the concentration of carboxylic groups is much higher in FEP and PFA than in PTFE, which is due to the lower crystallinity of the copolymers.

Electron beam irradiation of PTFE was performed in vacuum at elevated temperature above the melting point. The changes in the chemical structure were studied. The concentration of CF₃ branches was found to be much higher as compared to room temperature irradiation.

In a practical test PTFE micropowders functionalized by electron irradiation were compounded with epoxy resins, with polyoximethylene and with polyamides. Such compounds are characterized by very good frictional and wearing behaviour in dry-running tests.     

Synthesis of silver nanoparticles using dl-alanine for ESR dosimetry applications

The potential use of alanine for the production of nanoparticles is presented here for the first time. Silver nanoparticles were synthesized using a simple green method, namely the thermal treatment of silver nitrate aqueous solutions with dl-alanine. The latter compound was employed both as a reducing and a capping agent. Particles with average size equal to 7.5 nm, face-centered cubic crystalline structure, narrow size distribution, and spherical shape were obtained. Interaction between the silver ions present on the surface of the nanoparticles and the amine group of the dl-alanine molecule seems to be responsible for reduction of the silver ions and for the stability of the colloid. The bio-hybrid nano-composite was used as an ESR dosimeter. The amount of silver nanoparticles in the nanocomposite was not sufficient to cause considerable loss of tissue equivalency. Moreover, the samples containing nanoparticles presented increased sensitivity and reduced energetic dependence as compared with pure dl-alanine, contributing to the construction of small-sized dosimeters.     

Current and charge collector as e beam energy and dose meter for industrial use

Many parameters of interest for characterizing a high power processing electron beam in air can be measured using a charge density detector system.

A rugged detector head placed in or moved through an electron beam may be used to measure the effective beam energy, current density within the beam and charge delivered to the product plane.

The liquid cooled detector may also be used to calibrate routine dosimeter for electron beam use over the full range of doses and dose rates currently used for industrial purposes.

Further uses for the detector as an accelerator control sensor element are also discussed.     

Operational experience of a commercial scale plant of electron beam purification of flue gas

A commercial scale plant using electron beam irradiation was constructed to clean the flue gas from a coal fired thermal power plant at Chengdu in China. Operations began in September 1997 and the plant achieved its design performance with the satisfactory recovery of by-product fertilizer for agricultural use. Another commercial plant is now under construction at Nagoya, Japan and the operation will be started in November, 1999.     

Synthesis of colloidal SnSe quantum dots by electron beam irradiation

Water-soluble orthorhombic colloidal SnSe quantum dots with an average diameter of 4 nm were successfully prepared by a novel irradiation route using an electronic accelerator as a radiation source and hexadecyl trimethyl ammonium bromide (CTAB) as a surfactant. The quantum dots exhibit a large direct bandgap of 3.89 eV, greatly blue shifted compared with that of bulk SnSe (1.0 eV) due to the quantum confinement effect. The quantum dots show blue photoluminescence at ∼420 nm. The influence of CTAB on the growth of the quantum dots was investigated and a possible reaction/growth mechanism was proposed.     

Influence of electron beam pre-irradiation on the thermal behaviors of polyacrylonitrile

Thermal treatment of polyacrylonitrile pre-irradiated by electron beam was performed to investigate the radiation effects on thermally activated reactions. Thermal properties were characterized by differential scanning calorimetry and thermogravimetric analyses. Pre-irradiation lowers the onset temperature of reactions and alleviated the heat evolution process. Char yields (800 °C) of polyacrylonitrile increase significantly with increasing irradiation dose. FTIR was used to monitor the thermal reaction. The results reveal that the thermal reactions can be regulated by pre-irradiation dose. FTIR and UV-visible absorption spectra of pre-irradiation polyacrylonitrile illustrate the formation of -HCN-NCH- conjugation across the polymeric chains as a function of dose, which could improve the thermal behaviors of polyacrylonitrile.     

Investigation of antioxidant and electron beam radiation effects on the thermal oxidation stability of low-density polyethylene

Effect of various antioxidants on the thermal oxidation stability of LDPE and X-LDPE has been investigated. To achieve this purpose, miscellaneous commercial grade antioxidants such as Irganox 1010, Irganox1076, Irgafos168, Irganox B225, and Chimassorb 944 were selected. Then, formulations based on different content of antioxidant were prepared. The samples were crosslinked by exposure to electron beam irradiation. To assess the thermal oxidation stability of samples, oxidation induction time (OIT) test was accomplished on both the irradiated and unirradiated specimens. Ageing tests were carried out in order to evaluate the thermal oxidation stability of irradiated X-LDPE. The results indicate that Irganox 1010 is the most effective antioxidant amongst the selected ones, concerning thermal oxidation stability of LDPE, before and after aging test.     

Application of electron beam irradiation combined to conventional treatment to treat industrial effluents

A preliminary study to combine electron beam irradiation process with biological treatment was carried out. Experiments were conducted using samples from a governmental wastewater treatment plant (WTP) that receives about 20% of industrial wastewater, with the objective of destroying the refractory organic pollutants and to obtain a better performance of this plant. Samples from five different steps of WTP were collected and irradiated in the electron beam accelerator in a batch system with 5.0, 10.0 and 20.0 kGy doses. The main results showed a removal of 99% of all organic compound analysed in the industrial receiver unit (IRU) effluent and in the coarse bar screen (CBS) effluent with a 20 kGy dose, and for the medium bar screen (MBS) and primary sedimentation (PS) effluent a 10 kGy dose was sufficient. In the case of final effluent (FE), a dose of 5 kGy removed the remaining organic compounds and dyes present after biological treatment.     

Irradiation of ferrous ammonium sulfate for its use as high absorbed dose and low-temperature dosimeter

In the present paper, we study the response of crystalline ammonium ferrous sulfate as a function of the irradiation dose and temperature. The dose studied ranged from 33.5 to 546 kGy. The temperature regimen varied from 77 K (liquid nitrogen) to 311 K. The analysis of the samples was made by UV spectroscopy and EPR.The results show that the change in absorbance of the dosimeter was linear with respect to the absorbed dose in the range studied. There is a small influence of the irradiation temperature in the response of the iron salt. The dose rate and storage time after irradiation was of no importance in this application.     

Review on the production process and uses of controlled rheology polypropylene—Gamma radiation versus electron beam processing

Controlled rheology polypropylene grades are established commodities in the polymer processing market. However, new types, mainly the so-called high melt strength polypropylene (HMSPP) grades, are being introduced in the last two decades and radiation processing has played an important role. The melt strength properties of a polymer increases with molecular weight and with long-chain branching due to the increase in the entanglement level. As polypropylene (PP) is a linear polymer, the way to improve its elongational viscosity is by the production of a bi-modal polymer. Basell's patents claim the production of long-chain branching on PP by irradiating with electrons under oxygen free atmosphere, followed by two heating steps to allow radical recombination and annihilation reaction. Some other companies have issued patents using electron beam processing, but so far there is no actual production other than the Basell one. As a result of a research joint effort, IPEN, BRASKEM (the biggest Brazilian polymer producer) and EMBRARAD (the major Brazilian radiation processing center) developed a new process to produce HMSPP based on gamma processing. This paper will address some characteristics of each technology and the main industrial opportunities.     

Crosslinking of recycled polyethylene by gamma and electron beam irradiation

Recycling of polymeric materials is usually accompanied by degradation and deleterious properties. Irradiation crosslinking of recycling low density polyethylene by electron beam and gamma rays could be the solution to improve their properties. This paper presents a comparison on the effects of gamma and electron irradiation on virgin and recycled polyethylene. Their mechanical, thermal and chemical properties were analyzed. VPE samples shown higher crosslinking percentages than RPE samples in all range of doses studied, unirradiated RPE samples had higher values on their tensile properties than VPE. Percentage crystallinity was similar in all range of doses studied.     

Degradation of epoxy resins under high energy electron beam irradiation: Radio-oxidation

The degradation of two epoxy systems exposed to electron beam irradiation in oxygen atmosphere has been studied and compared to our previous results obtained under helium atmosphere. A multi-scale approach to the degradation has been carried out using a variety of analytical methods including solid state NMR spectroscopy, 2D-WISE experiments, SEC measurements and infrared spectroscopy associated with chemical derivatisation treatments. It is shown that the degradation of both polymers is governed by radiolytic processes which involve chain scissions. The formation of oxidation products, mainly carboxylic acid chain ends, was shown at the surface of the irradiated film. Oxidative degradation is limited to the first 20 μm of the film due to the low oxygen diffusion coefficient in epoxy polymers combined with the high dose rates of irradiation.