Comparison of degradation effects induced by gamma radiation and electron beam radiation in two cable jacketing materials

The radiation degradation behavior of commercial low density polyethylene (LDPE) and ethylene–vinylacetate (EVA) cable materials has been investigated. The changes of mechanical properties, thermooxidative stability and density exhibit different radiation stability towards ⁶⁰Co-gamma radiation and 160 keV electron beam radiation. This difference reflects much higher penetration of the gamma radiation through the polymeric material as a function of sample thickness. These results are discussed with respect to the role of beta radiation during design basis events in a nuclear power plants. In case when total accidental design basis event (DBE) dose (involving about 80% soft beta radiation) is simulated by ⁶⁰Co-gamma radiation the conservatism is reached.     

An investigation on focused electron/ion beam induced degradation mechanisms of conjugated polymers

Irradiation damage, caused by the use of beams in the electron microscopes, leads to undesired physical/chemical material property changes or uncontrollable modification of structures that are being processed. Particularly, soft matter such as polymers or biological materials is highly susceptible and very much prone to react on irradiation by electron and ion beams. The effect is even higher when materials are subjected to energetic species such as ions that possess high momentum and relatively low mean path due to their mass. Especially when Ga(+) ions (used as the ion source in Focused Ion Beam (FIB) instruments) are considered, the end-effect might even be the total loss of the material's properties. This paper will discuss the possible types of degradation mechanisms and defect formations that can take place during ion and electron beam irradiation of the conjugated polymers: e.g. polyfluorene (PF) and poly-3-hexylthiophene (P3HT) thin films. For the investigation of the irradiation induced degradation mechanisms in this study, complementary analytical techniques such as Raman Spectroscopy (RS), Infrared Spectroscopy (IR), Electron Energy Loss Spectroscopy (EELS), Atomic Force Microscopy (AFM), and Fluorescence Microscopy including Photoluminescence (PL) and Electroluminescence (EL) Microscopy were applied.     

Influence of radiation temperature on the crosslinking of nitrile rubber by electron beam irradiation

Nitrile rubber with 18% acrylonitrile content in presence and absence of polyfunctional monomers like trimethylolpropane triacrylate (TMPTA), tripropyleneglycol diacrylate (TPGDA), tetramethylolmethane tetraacrylate (TMMT) and m-phenylene bismaleimide was subjected to electron beam irradiations at different temperatures. The structural changes with different doses of radiations were investigated with the help of FTIR spectroscopy (in the ATR mode), dynamic mechanical thermal analysis and sol–gel analysis. There was a decrease in the concentration of olefinic groups for this elastomer on radiation at high temperature as compared to the room temperature. The increase in crosslinking at elevated temperature was also revealed by the increase in % gel content and dynamic storage moduli with radiation dose. The lifetime of spurs, an important criterion for overlapping of spurs, was determined for both grafted and ungrafted nitrile rubber using a mathematical model. The ratio of scissioning to crosslinking for nitrile rubber was determined using Charlesby–Pinner equation. The mechanical properties were studied and the tensile strength was found to increase with grafting of polyfunctional monomers on irradiation at high temperature.     

Effect of dose rate on degradation of 2,6-dichlorophenol by electron beam irradiation

The effects of different dose rates on the degradation of 2,6-dichlorophenol (2,6-DCP) in aqueous solution were investigated at about 2?×?10⁴ Gy absorbed dose, using a 10 MeV electron beam accelerator. It was found that the removal efficiency decreased with increasing dose rate at all initial concentrations of 0.5, 1 and 2 g L^?1, and the effect was significantly diminished by addition of P25 TiO₂ nanoparticles. Alkaline medium were unfavorable for degradation of 2,6-DCP. Hydrogen peroxide (H₂O₂) could promote the removal efficiency at a lower dose rate rather than at a higher one.

     

Decomposition and decoloration of a direct dye by electron beam radiation

The wastewaters released by textile industries to the environment contain hazardous compounds like toxic refractory dye stuff at high concentration. In this study, electron beam irradiation-induced decoloration and decomposition of C.I. Direct Black 22 aqueous solutions were investigated. The influences of absorbed doses and initial dye concentration on the percent of decoloration, COD and pH of the solutions are described. The results show that the direct dye solutions can be effectively degraded by electron beam irradiation.     

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 study on size effect of carboxymethyl starch nanogel crosslinked by electron beam radiation

The formation of carboxymethyl starch (CMS) nanogel with 50 nm less particle size was carried out through a radiation crosslinked process on the electron beam (EB) linear accelerator. Changes of intrinsic viscosities and weight averaged molecular weight in the CMS concentration, which ranged from 3 to 10 mg ml^?1 in absorbed doses were investigated. There were some new peaks in the ¹H NMR spectra of CMS nanogel compared with those of CMS polymer. These results were anticipated that the predominant intramolecular crosslinking of dilute CMS aqueous solution occurred while being exposed to a short intense pulse of ionizing radiation. Hydrodynamic radius (often called particle size, R_h) and distribution of particle size were measured by a dynamic light scattering technique. The radiation yield of intermolecular crosslinking of CMS solution was calculated from the expression of G_x (Charlesby, 1960, Jung-Chul, 2010). The influence of the “size effect” was demonstrated by testing culture of Lactobacillus bacteria on MRS agar culture medium containing CMS nanogel and polymer. Results showed that the number of Lactobacillus bacteria growing on nanogel containing culture medium is about 170 cfu/ml and on polymer containing culture medium is only 6 cfu/ml.     

Observation of radially polarized terahertz radiation generated by a sub-picosecond electron beam

The fundamental property of radially polarized terahertz radiation, which is axial symmetry of the polarization state in the radial direction, was measured with a Schottky diode detector and with a terahertz camera and wire-grid linear polarizer. Radially polarized terahertz radiation was generated from coherent transition radiation using a 30-MeV sub-picosecond electron beam. Bow-tie intensity distributions, aligned along the polarization direction, were clearly observed with the terahertz camera and could be rotated by changing the direction of the linear polarizer. The measured intensity distribution agreed with the calculated value. A video of the data can be found online.     

The effect of orientation on the radiation induced degradation of polymers

A study has been made of the effect of orientation on the oxidative degradation of poly(vinylchloride) (PVC), low density polyethylene (LDPE) and high density polyethylene (HDPE) under the influence of γ- and u.v.-radiation. The effect of drawing in PVC is to increase the rate of oxidative degradation; in LDPE and HDPE, this rate decreases (especially for HDPE) both under u.v. and γ-radiation.     

Effect of electron beam radiation dose on the foam formation in pre-ceramic polymer

Methylsilicone resin as a polymer precursor for a SiOC ceramic material was cured and foamed by electron beam (EB) irradiation in air prior to the pyrolysis under an inert atmosphere. Methylsilicone foams were obtained without additional foaming agent when exposed to accelerated electrons with radiation doses up to 9 MGy and dose rate of 2.8 kGy/s. During irradiation the polymer was melted and simultaneously gaseous products were formed by the methyl group oxidation and by the poly-condensation crosslinking reactions. The formed gases could not escape from the molten polymer and began to aggregate into bubbles. The effect of the radiation dose on the polymer foam molecular structure, the gel fraction and the ceramic yield was analyzed. The results indicate that the maximum amount of crosslinking in methylsilicone, when EB radiation is used, occurred between 1.0 and 2.0 MGy radiation dose. Methylsilicone foams were pyrolysed in N₂ atmosphere at temperatures of 1200 and 1500 °C, resulting in amorphous SiOC and partially crystalline ceramic foams, respectively. A porosity of ~84% was achieved in the pyrolyzed foams, with cell size ranging from 30 to 300 μm and density of about 0.31 g cm^?3.     

Atomic structural rearrangements induced by electron beam heating of coalesced palladium particles

Change in the atomic surface structure of small coalesced palladium particles is shown by High Resolution Electron Microscopy imaging; these atomic surface restructuration events during observation are induced by the electron beam irradiation. They include atom evaporation from specific crystallite facets, surface diffusion of atoms which consecutively affects the particle morphology especially in the case of multiple-twinned particles and the growth of crystallite parts and resulting strains.     

Network characteristics of hydrogenated nitrile butadiene rubber networks obtained by radiation crosslinking by electron beam

The effects of high-energy radiation on hydrogenated nitrile butadiene rubber (HNBR) copolymer structure and properties were studied. Characterization by FTIR spectroscopy, swelling and mechanical measurements of irradiated and un-irradiated sample permit us to correlate the change in structure with properties. The modifications obtained are dependent on the radiation dose of the incident electron beam. FTIR spectroscopy in absorption mode shows that irradiation of HNBR first induces trans-vinylene bond formation and secondly small amounts of carbonyl (CO) groups. Moreover, more significant changes were observed with swelling method and mechanical behaviour showing the effect of crosslinking on the elastomer.     

Electron beam induced degradation of clopyralid in aqueous solutions

The degradation characteristics of clopyralid irradiated by electron beam (EB) was studied in aqueous solutions. The effects of factors, such as initial clopyralid concentrations, addition of radicals scavenger, initial solution pH and addition of H₂O₂, were investigated on clopyralid degradation efficiency and mechanism. It was found that the EB-radiolysis was an effective way to degrade clopyralid and its degradation rate decreased with the increasing of substrate concentration. In the investigated initial concentrations range of 100?C400 mg L^?1, the radiolytic degradation of clopyralid followed a pseudo-first kinetic order. The results from addition of radicals scavenger indicated that both ^?OH and e _aq ^? played significant roles in the degradation of clopyralid. Furthermore, the alkaline condition and addition of H₂O₂ (<10 mM) in the solution also slightly enhanced the efficiency of clopyralid degradation. The ion chromatography analysis showed that some organic acids (formic acid, acetic acid and oxalic acid) were formed, while the completely dechlorination of the substrate was achieved and organic nitrogen was recovered in the form of ammonium and nitrate ions during the irradiation process.     

Increase in crystallinity in poly(vinylidene fluoride) by electron beam radiation

We examine the influence of high-energy radiation and subsequent aging and orientation on the degree of crystallinity of poly(vinylidene fluoride) (PVDF) films. In particular, PVDF films were exposed to electron beam radiation (doses up to 50 Mrad) and aged at room temperature for varying lengths of time followed by uniaxial orientation. The degree of crystallinity of these films was found to increase significantly with increasing radiation dose. In addition, a further substantial increase in the degree of crystallinity was observed upon subsequent aging of irradiated films at room temperature. Upon orientation, in addition to a further rise in the degree of crystallinity, the crystallites were observed to undergo the α form → β form transformation, the latter phase being the polar phase effective for piezo-electric/pyroelectric activity.     

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.     

Investigation of the electron beam induced transformation of Cu3 N-films

Homogeneous films of metastable Cu₃N were deposited on Si-<100> wafers at 90°?C by means of reactive magnetron sputtering ion plating. Under electron bombardment with a focused beam at high current (> 700 nA, 15 keV) these films transform into metallic Cu and N₂. The depletion of N was measured quantitatively by EPMA. Structures with a lateral size of 2 μm consisting of metallic copper were written into the Cu₃N films. AFM surface scans revealed a vertical growth of the columnar grains of the Cu₃N film due to the electron bombardment.     

The characterization of latex particles prepared by pulsed electron beam induced emulsion polymerization

The emulsion polymerization of styrene (St) and methyl methacrylate (MMA) induced by 10 MeV pulsed electron beams (PEB) was investigated. The monomer conversion of MMA and St was found to be very low so that the final prepared poly(methyl methacrylate) (P(MMA)) and polystyrene (PS) latex particles exhibit porous structures, as verified by TEM and SEM observations. The results of dynamic light scattering (DLS) and gel permeation chromatography (GPC) showed that both the particle size and the molecular weight of PS and PMMA latexes decrease with the increase of the absorbed dose. However, the molecular weights and the particle sizes of the PS and PMMA latexes change differently with the irradiation time. This work indicated that emulsion polymerization induced by high energy electron beam has an advantage over that induced by γ-ray or chemical initiators in the preparation of latex with a low molecular weight and porous structure.     

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.     

Modelling molecular weight changes induced in polydimethylsiloxane by gamma and electron beam irradiation

A commercial linear polydimethylsiloxane (PDMS) was subject to gamma irradiation under vacuum and in air, as well as to accelerated electron beam radiolysis (EB). All irradiation treatments were done at room temperature. The molecular weight changes induced by the radiation processes have been investigated using size exclusion chromatography (SEC) with refraction index (RI) and multi angle laser light scattering (MALLS) detectors to obtain the number and weight average molecular weights of the irradiated samples.

The analysis of the data indicates that crosslinking reactions predominated over scission reactions in all cases. Gamma irradiation under vacuum was the most efficient process within the analyzed dose range, reaching the gel point earlier. Irradiation in the presence of oxygen induces oxidative effects, both in gamma and EB irradiations. A previously developed mathematical model of the irradiation process that accounts for simultaneous scission and crosslinking and allows for both H and Y crosslinks fitted well the measured molecular weight data.     

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.