Study on the 1,3,5-triazine gamma-radiolysis

Triazines are a class of molecules which have been found in meteorites such as Orgueil meteorite. Despite their poor resistance to UV radiation, these molecules survived millions of years inside a meteorite. The present work is dedicated to the examination of the radiation resistance of the simplest sym-triazine: 1,3,5-triazine. The crystals of this molecule have been irradiated with γ-radiation at 50 and 350 kGy and were studied by electronic absorption spectroscopy, liquid chromatography, FT-IR spectroscopy and differential scanning calorimetry (DSC). All the data suggest the relatively low stability of this molecule to high energy radiation. The resulting products from radiolysis are formamidine together with triazine dimers and oligomers. Other radiolysis products are H₂, CH₄, HCN and other gases.     

Investigation of radiochemical conversions in extraction systems based on tributyl phosphate

The use of halogenated organic compounds under the effect of ionizing radiation requires a comprehensive knowledge of their radiation stability. There is little experimental evidence on the radiolysis of fluorine-containing organic compounds in the literature, while a theoretical generalization enabling one to predict the main radiolysis pathways is completely lacking. This paper is concerned with the identification of stable radiolysis products of trichloromethyl-1,1,2-trifluoro-2,2-dichloroethyl ether (C₃F₃Cl₅ O), γ-irradiated separately and the extraction system based on tributyl phosphate. Practically all the C₃F₃Cl₅O radiolysis products were identified with the aid of gas-liquid chromatography, GC-MS, IR, UV and NMR spectroscopy and elemental analysis. Upon C₃F₃Cl₅O radiolysis, the formation of CCl₄, Cl₂, COCl₂, C₂ Cl₆, freons of various composition and long-chained ethers like CFCl₂−CF₂−O−CCl₂−CCl₃ takes place. The identification of radiolysis products allows to draw well-founded conclusions on the mechanism of C₃F₃Cl₅O radiolysis, representing a wide class of chlorine- and fluorine-containing organic compounds.     

Neutron activation analysis by combined capture and decay gamma-spectrum method

The usual method of the neutron activation analysis is performed by the measurement of the characteristic nuclear radiations of the produced radioactive isotope by neutron irradiation. An advance in this field has recently been proposed in which the prompt capture γ-rays are observed in addition to the nuclear radiation of the produced nucleus. The characteristic energy spectra of these two kinds of γ-radiations are the main basis for the combined activation analysis method. The experimental setup consists of a γ-radiation pulse height energy spectrum system which is synchronized with a pulsing neutron generator of ‘D—T’ or ‘D—D’ reaction. The present results indicate that a qualitative and semi-quantitative determination of a number of elements is feasible, with an overall error of 10–15%.     

Radiolysis and corrosion of238Pu-doped UO2 pellets in chloride brine

Deaerated 5 M NaCl solution is irradiated in the presence of UO₂ pellets with α-radiation from²³⁸Pu. Experiments are conducted with²³⁸Pu doped pellets and others with²³⁸Pu dissolved in the brine. The radiolysis products and yields of mobilized U and Pu from the oxidative dissolution of UO₂ are determined. Results found for radiolysis products and for the oxidation/dissolution of pellets immersed in Pu containing brine are similar to results for Pu doped pellets, where the radiation chemical processes occur only in the liquid layer of some 10 σm thickness adjacent to the pellet. The yield of radiolysis products is comparable to earlier results, that of mobilized U from the pellets is < 1% of the total amount of oxidized species. Thus, the radiation chemical yield (G-value) for mobilized hexavalent U is < 0.01 ions/100 eV. In spite of the low radiation yield for the corrosion, the rate of UO₂dissolution is higher than expected for the concentrations of long-lived oxidizing radiolysis compounds found in the solutions.     

γ-Radiation Effects on the Thermal Stability of Bovine γ-Globulin

Low-dose γ-radiation produces subtle effects on bovine γ-globulin, as revealed by calorimetric investigations carried out on concentrated aqueous solutions. The irradiation rate used seems below the threshold that allows complete protein denaturation; the denaturation temperature, T_d, remained unaffected; nonetheless, modifications of the shape of the calorimetric signal reveal that other changes, such as the dissociation of protein oligomers, could take place. This revised version was published online in July 2006 with corrections to the Cover Date.     

Detection and investigation of oscillations of the rate of radiation-induced solid-state chain reactions at low temperatures

The data on the detection and investigation of rate oscillations of radiation-induced (⁶⁰Co γ-radiation) cryochemical solid-state chain reactions are reviewed. Self oscillation regimes were observed for various reactions (ethylene hydrobromination, polymerization, and copolymerization) in the crystalline and glassy states both in the field of γ-radiation and as the post-effect recorded when the samples were warmed. The recent experimental data on the unusual oscillations of the polymerization rate of crystalline formaldehyde at 5–30 K are discussed. The mechanical factor (brittle disintegration) is proposed to be responsible for these oscillations.     

Influence of polyether ring size and of the nature of substituents on the yields of paramagnetic centers in γ-irradiated mono-and dibenzosubstituted crown ethers at 77 K

Intermediates stabilized in γ-irradiated mono-and dibenzosubstituted crown ethers are studied by ESR spectroscopy at 77 K. PhO radicals and radicals with H-atom abstraction from polyether ring are the main products at low temperature γ-radiolysis. The nature of radicals produced in radiolysis and the yield of radicals,G _R depend on macroring size and on the number of aromatic substiuents. Negative deviation from additive in function ofG _R versus ε of substituents is an evidence of efficient transfer of adsorbed energy to the π-system of aromatic group.     

Radiolysis of L- and D-Monosaccharides

The effects of ⁶⁰Co -radiation on D-glucose, L-glucose, D-galactose, L-galactose, D-mannose, and L-mannose were studied. The yields of gaseous radiolysis products were determined. The curves of radical buildup and decay in crystalline samples were obtained. Conclusions on the relative radiation stability of these D- and L-monosaccharides to the action of nonpolarized radiation were drawn.     

Effect of gamma-irradiation on adsorption properties of Slovak bentonites

One of the basic prerequisites for the use of bentonite as engineering barrier in deep geological repositories for radioactive waste and spent nuclear fuel is their stability against ionizing radiation stemming from radionuclides present in radioactive waste and spent nuclear fuel. The aim of this study was to compare the changes in the adsorption properties of selected Slovak bentonites in relation to uranium fission products (¹³⁷Cs and ⁹⁰Sr), prior to and after irradiation of bentonites with a ⁶⁰Co γ-source and specifying the changes in the structure of Slovak bentonites induced by γ-radiation. The changes in irradiated natural forms of Slovak bentonites and the changes in their natrified analogues and fractions with different grain sizes were studied from five Slovak deposits: Jelšovy potok, Kopernica, Lastovce, Lieskovec and Dolná Ves. The EPR spectra of bentonites from deposits Jelšovy potok and Lieskovec with absorbed doses of 10⁴ and 10⁵ Gy γ-rays showed no changes in the structure of the studied Slovak bentonites. The changes, which in terms of structure destabilization can be considered insignificant, occurred only in bentonites with absorbed doses of γ-radiation as much as 1 MGy. The absorbed dose of 1 MGy γ-radiation did not have an effect on the adsorption of cesium on every studied bentonite. Changes that can also be regarded as insignificant occurred only during strontium adsorption, especially on Fe–bentonite from deposit Lieskovec and Ca–Mg–bentonite from deposit Jelšovy potok, when an increase in the adsorption capacity occurred. Attention should be paid in further research of this topic which would require carrying out experiments on bentonite samples with absorbed doses higher by several orders of magnitude.     

FTIR study of gamma-irradiated cis-1,4-polyisoprene

The effect of γ-irradiation on the structure and oxidation of cis-1,4-polyisoprene is investigated by ATR-FTIR technique. This method provides the valuable insight into the type of oxidation products produced and the extent and nature of intramolecular cyclization and chain scission reactions. The formation of ketones, alcohols and/or ethers, and hydroperoxides is apparent already at small doses of γ-radiation and it increases with the exposure time significantly. At the highest dose of 309 kGy a decrease in the intensity of C=O stretching mode of ketones (1717 cm⁻¹) was observed while the overall area of the band remained the same as in the case of 188 kGy dose. The shoulders observed at 1740 cm⁻¹ and 1772 cm⁻¹ could be assigned to C=O stretching frequency of esters and five-membered-ring lactones, respectively. Higher doses of γ-radiation also cause the formation of two relatively strong bands in the region of conjugated double bonds. These could origin from the aromatic products or cycloenes with one double bond formed by cyclization and chain scission processes.     

Latex interpenetrating polymer networks of epoxidised natural rubber/poly(methyl methacrylate): an insight into the mechanism of epoxidation

Composite latex particles consisting of epoxidised natural rubber (ENR) and poly(methyl methacrylate) (PMMA) were synthesised to obtain interpenetrating polymer networks. Among the ENR latices having 9 to 36 mol% epoxide, prepared by in situ reaction using performic acid, the ENR latex with 25 mol% epoxide was selected for prevulcanisation by sulphur or γ-radiation system. The swelling ratios of sheets cast from the sulphur-prevulcanised ENR (SPENR) latices decreased with increasing prevulcanisation time while those cast from the γ-radiation-prevulcanised ENR latices were also inversely proportional to the irradiation dose. By applying the phase transfer/bulk polymerisation/transmission electron microscopy (TEM) technique, a homogeneous network structure in each of the SPENR particles and also a relative dense network near the surface in γ-radiation (RV) ENR particle were noticed. When 10 to 30 wt% of MMA swollen in ENR particles was polymerised, the mesh structure was observed in each particle. The dense network near the RVENR particle surface might be used as additional evidence that the degree of epoxidation and, hence, the presence of swollen n-butyl acrylate in the outer zone were higher than in the internal region.     

Gamma radiolysis of EDTA in a simulated, mixed nuclear waste

The effects of γ-irradiation on EDTA degradation have been studied. A simulant of Hanford's complex concentrate was prepared by adding EDTA to an inorganic matrix which was formulated based on past analyses of the actual Hanford complex concentrate waste. For, the radiolysis study, aliquots of the simulated waste were then γ-irradiated. Each waste sample was analyzed to monitor the appearance of degradation products. Based on the results of this study, an assessment of the impact of EDTA degradation on the management of mixed wastes is offered.     

The determination of Br,Ag and I in pharmaceuticals using X-ray fluorescence excited by gamma sources

The possibility of using γ-radiation sources for the X-ray fluorescence analysis of Br, Ag, and I was studied on model samples. The results were applied for the determination of these elements in pharmaceutical products. The optimum channel range was selected and the accuracies obtainable with various types of radiation sources were compared. For routine analysis of pharmaceutical products and other substances of similar composition, the most suitable radiation sources are:¹²⁵I for the determination of low concentration of bromine;¹⁵³Gd for the determination of silver; and²⁴¹Am for that of iodine.     

Radiolysis of aqueous DCH18C6 solutions at 77 K

Low-temperature (77 K) γ- and X-ray radiolysis of aqueous DCH18C6 solutions was studied by ESR-spectroscopy. OH radicals, trapped electrons and macrocyclic radicals -CH₂-CH-O- resulting from H-atom abstraction from methylene groups of polyether ring were identified as predominant radiolysis products. Increasing the crown ether concentration in aqueous solution leads to the growth of relative yields of the trapped electron and macrocyclic radicals as well as the decrease of that of hydroxyl radical. Neither radical products of macrocycle rupture nor H-atom abstraction from cyclohexane rings were observed.     

Thermal Stability of γ-irradiated Tolbutamide

The thermal stability of tolbutamide before and after exposure to various γ-radiation doses was investigated. The data were followed by studying DTA, X-ray diffraction, IR, and UV absorption spectra before and after γ-irradiation. The results obtained were promising, and were explained, and discussed on the basis of γ-enhanced stabilization through recombination of free radicals. This revised version was published online in August 2006 with corrections to the Cover Date.     

A detailed analysis of the properties of radiolyzed proteinaceous amino acids

The thermal behaviour of 21 proteinaceous l-amino acids either as pristine samples and also as radiolyzed (3.2 MGy) samples was studied with the differential scanning calorimeter. The onset and peak melting point as well as the melting enthalpy of all samples before and after the radiation treatment was measured and reported. The residual amount of each amino acid survived to the radiation dose of 3.2 MGy (N _γ) was measured from the melting enthalpies before and after radiolysis and hence the radiation resistance of each amino acid has been determined. The radiolysis causes a systematic reduction of the melting enthalpy and a shift of the onset and peak melting point to lower values. It is shown that N _γ does not correlate with the melting points of the amino acids but shows a correlation with the entity of the shift of the melting point peaks occurred after radiolysis. Such correlation instead does not exist between the N _γ parameter and the onset melting points of the amino acids. An explanation of such lack of correlation was given. Furthermore, a general relationship has been found between the amino acids melting point peak measured on pristine samples and the melting point peaks after solid state radiolysis. Such relationship can be used to predict roughly the expected melting point after radiolysis at 3.2 MGy of any given amino acid. The last part of the study was dedicated in the attempt to find a correlation between the N _γ parameter and the amount of the amino acids survived the radiolysis R _γ as measured by spectropolarimetry (ORD spectroscopy). A general trend was found in the connection between the N _γ and R _γ parameters but not a very strong correlation.     

Radiation-initiated telomerization of tetrafluoroethylene in 1,2-dibromotetrafluoroethane

The kinetics of the radiation telomerization of tetrafluoroethylene in 1,2-dibromotetrafluoroethane has been studied. It has been shown that the process occurs very efficiently in the perfluorinated solvent; small doses of γ-radiation (~2 kGy) are required for the complete conversion of the monomer. Telomers with a chain length of 120–360 tetrafluoroethylene units and high thermal stability are formed in the reaction. The structure and properties of the telomers have been studied by IR spectroscopy, thermogravimetry, and elemental analysis.     

Synthesis and flocculation performance of graft and random copolymer microgels of acrylamide and diallyldimethylammonium chloride

Graft (from linear homopolymers) and random (from a linear random copolymer) copolymer microgels of diallyldimethylammonium chloride (DADMAC) and acrylamide were synthesized via a free-radical mechanism using a γ-radiation technique. These copolymer microgels were evaluated as flocculants on a model dilute TiO₂ colloid suspension using a turbidimeter and a disc centrifuge photosedimentometer, and their performances were compared with the linear homopolymers and their blends. It was found that microgels produced after an appropriate irradiation time showed improved flocculation behavior over their nonirradiated linear counterparts. The graft microgels performed better than the corresponding random microgels. For a γ-radiation dosage of 100 krad/h, the graft microgels obtained by irradiating a 30% DADMAC (by weight) homopolymer blend for 3 h showed the maximum reduction in the relative turbidity of the TiO₂ suspension as well as the largest fraction of larger particles flocculated. Received: 18 May 1999 Accepted in revised form: 1 June 1999     

Radiation-Thermal Decomposition of NO2–NO Mixtures in a 60Co γ-Radiation Field

The effect of nitrogen monoxide (up to 60 wt %) on the radiation-thermal decomposition of a dissociating mixture based on N₂O₄ in a ⁶⁰Co -radiation field was studied over the temperature range 200–300° at a pressure of 2 MPa. A comparison of the experimental results with data calculated using an additive mathematical model of radiolysis and data obtained in previous studies on processes in an n,-radiation field led to the conclusion that the role of intermolecular energy-transfer processes is insignificant. The currently available mathematical model adequately describes the radiolysis of nitrogen oxides over wide temperature and pressure ranges.