Degradation by Electron Beam Irradiation of Some Composites Based on Natural Rubber Reinforced with Mineral and Organic Fillers.

Composites based on natural rubber reinforced with mineral (precipitated silica and chalk) and organic (sawdust and hemp) fillers in amount of 50 phr were obtained by peroxide cross-linking in the presence of trimethylolpropane trimethacrylate and irradiated by electron beam in the dose range of 150 and 450 kGy with the purpose of degradation. The composites mechanical characteristics, gel fraction, cross-linking degree, water uptake and weight loss in water and toluene were evaluated by specific analysis. The changes in structure and morphology were also studied by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Based on the results obtained in the structural analysis, possible mechanisms specific to degradation are proposed. The increasing of irradiation dose to 450 kGy produced larger agglomerated structures, cracks and micro voids on the surface, as a result of the degradation process. This is consistent with that the increasing of irradiation dose to 450 kGy leads to a decrease in crosslinking and gel fraction but also drastic changes in mechanical properties specific to the composites' degradation processes. The irradiation of composites reinforced with organic fillers lead to the formation of specific degradation compounds of both natural rubber and cellulose (aldehydes, ketones, carboxylic acids, compounds with small macromolecules). In the case of the composites reinforced with mineral fillers the degradation can occur by the cleavage of hydrogen bonds formed between precipitated silica or chalk particles and polymeric matrix also.

Comparative Study of γ- and e-Radiation-Induced Effects on FBGs Using Different Femtosecond Laser Inscription Methods.

This work presents an extensive, comparative study of the gamma and electron radiation effects on the behaviour of femtosecond laser-inscribed fibre Bragg gratings (FBGs) using the point-by-point and plane-by-plane inscription methods. The FBGs were inscribed in standard telecommunication single mode silica fibre (SMF28) and exposed to a total accumulated radiation dose of 15 kGy for both gamma and electron radiation. The gratings' spectra were measured and analysed before and after the exposure to radiation, with complementary material characterisation using Fourier transform infrared (FTIR) spectroscopy. Changes in the response of the FBGs' temperature coefficients were analysed on exposure to the different types of radiation, and we consider which of the two inscription methods result in gratings that are more robust in such harsh environments. Moreover, we used the FTIR spectroscopy to locate which chemical bonds are responsible for the changes on temperature coefficients and which are related with the optical characteristics of the FBGs.

Response of Various Yb3+-Doped Oxide Glasses to Different Radiation Treatments.

The radiation effects of electrons and protons on the spectroscopic and optical properties of oxide glasses doped with Yb3+ in various glass systems were investigated to understand the impact of the glass composition on the glass photo-response. Changes in the optical and emission properties were seen after the radiation treatment, and the magnitude of the changes depended on the irradiation source and dose. For all the investigated materials, the absorption coefficients in the 200-550 nm range increase post-irradiation, revealing the formation of defects in the glasses during the irradiation. While the spectroscopic properties of the tellurite glass remain unchanged, a small reduction in the Yb3+ emission intensity was seen after irradiating the phosphate, borosilicate, and germanate glasses, indicating that a reduction of Yb3+ to Yb2+ might occur in these glasses during the radiation treatment. The changes in the optical and spectroscopic properties after proton irradiation are small as they are localized at the surface of the glasses due to the shallow penetration depth of the proton in the glass. Even though the doses are small, the electron irradiation produces larger changes in the optical and spectroscopic properties since the electrons penetrate the entire volume of the glasses. All the changes in the optical and spectroscopic properties of the glasses were successfully reversed after a short heat treatment revealing the reversible nature of the photo-response of the investigated glasses.

Water Absorption Kinetics in Composites Degraded by the Radiation Technique.

Rubber-based wastes represent challenges facing the global community. Human health protection and preservation of environmental quality are strong reasons to find more efficient methods to induce degradation of latex/rubber products in order to replace devulcanization, incineration, or simply storage, and electron beam irradiation is a promising method that can be can be taken into account. Polymeric composites based on natural rubber and plasticized starch in amounts of 10 to 50 phr, obtained by benzoyl peroxide cross-linking, were subjected to 5.5 MeV electron beam irradiation in order to induce degradation, in the dose range of 150 to 450 kGy. A qualitative study was conducted on the kinetics of water absorption in these composites in order to appreciate their degradation degree. The percentages of equilibrium sorption and mass loss after equilibrium sorption were found to be dependent on irradiation dose and amount of plasticized starch. The mechanism of water transport in composites was studied not only through the specific absorption and diffusion parameters but also by the evaluation of the diffusion, intrinsic diffusion, permeation, and absorption coefficients.

Electron Beam Irradiation: A Method for Degradation of Composites Based on Natural Rubber and Plasticized Starch.

Polymeric composites based on natural rubber (NR) and plasticized starch (PS) obtained by peroxide cross-linking have been subjected to electron beam irradiation in order to investigate their degradation. The amount of PS ranged from 10 to 50 phr and the irradiation dose from 150 to 450 kGy. Irradiation was performed in atmospheric conditions using a linear electron accelerator of 5.5 MeV. Changes in chemical, physical, structural, and morphological properties of composites were correlated with variables, such as PS loading and irradiation dose. Thus, mechanical properties, gel fraction, cross-linking degree, water uptake, weight loss in toluene/water were compared with those obtained before irradiation. The changes in structure and morphology were studied by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Both PS loading and irradiation dose were found to be responsible for the degradation installing. Moreover, it has been shown that at the dose of 450 kGy, chain scission is dominant over cross-linking.

Water Absorption Kinetics in Natural Rubber Composites Reinforced with Natural Fibers Processed by Electron Beam Irradiation.

Natural rubber composites reinforced with hemp, flax, and wood sawdust were obtained by irradiation at room temperature with an electron beam of 5.5 MeV in order to meet the actual need for new materials that are environmentally friendly and safe for human health. The natural fibers loading was between 5 and 20 phr and the processing doses were between 75 and 600 kGy. The kinetics of water absorption in these materials were studied. The water diffusion was analyzed through Fick's law. The water absorption parameters (Qt and Qeq), diffusion parameters (k and n), diffusion coefficient (D), intrinsic diffusion coefficient (D*), sorption coefficient (S), and permeation coefficient (P) have depended on the fiber nature, amount used in blends, and irradiation dose. The obtained results showed that not in the case of each type of fiber used, the water absorption could be correlated with the specific cellulose and hemicellulose content, due to the changes induced by the electron beam.

A Method to Improve the Characteristics of EPDM Rubber Based Eco-Composites with Electron Beam.

A natural fiber reinforced composite, belonging to the class of eco composites, based on ethylene-propylene-terpolymer rubber (EPDM) and wood wastes were obtained by electron beam irradiation at 75, 150, 300, and 600 kGy in atmospheric conditions and at room temperature using a linear accelerator of 5.5 MeV. The sawdust (S), in amounts of 5 and 15 phr, respectively, was used to act as a natural filler for the improvement of physical and chemical characteristics. The cross-linking effects were evaluated through sol-gel analysis, mechanical tests, and Fourier Transform Infrared FTIR spectroscopy comparatively with the classic method with dibenzoyl peroxide (P) applied on the same types of samples at high temperature. Gel fraction exhibits values over 98% but, in the case of P cross-linking, is necessary to add more sawdust (15 phr) to obtain the same results as in the case of electron beam (EB) cross-linking (5 phr/300 kGy). Even if the EB cross-linking and sawdust addition have a reinforcement effect on EPDM rubber, the medium irradiation dose of 300 kGy looks to be a limit to which or from which the properties of the composite are improved or deteriorated. The absorption behavior of the eco-composites was studied through water uptake tests.

Hybrid technology with microwaves, electron beams and catalysts for VOCs removals.

This work presents a hybrid technology and two hybrid installations (HI-1 and HI-2) for volatile organic compounds (VOCs) removal using successive or simultaneous microwave (MW) irradiation, electron beam (EB) irradiation, and catalytic oxidation. HI-1 is designed for successive EB and MW irradiation with two distinct reactors, both containing a catalyst inside. HI-2 is designed for simultaneous EB and MW irradiation in the same reactor containing a catalyst. Real synergistic effects between non-thermal plasma (NTP) and catalysis were obtained by introducing the catalyst into the irradiation zone, i.e. into the MW reactor EB reactor or into a reactor in which both EB and MW are injected.

Combined effects of microwaves, electron beams and polyfunctional monomers on rubber vulcanization.

This paper presents comparative results obtained by conventional vulcanization with benzoyl peroxide (CV-BP), separate electron beam vulcanization (EB-V) and simultaneous electron beam and microwave vulcanization (EB+MW-V) applied to two kind of rubber samples: EVA (ethylene vinyl acetate) rubber-sample (EVA-sample) and EPDM (ethylene-propylene terpolymer) rubber-sample (EPDM-sample). The EVA-samples contain 61.54% EVA Elvax 260, 30.77% carbon black, 1.85% TAC (triallylcyanurate) polyfunctional monomer and 5.84% filler (zinc oxide, stearic acid, polyethylene glycol and antioxidant). The EPDM-samples contain 61.54% EPDM Nordel 4760, 30.77% carbon black, 1.85% TMPT (trimethylopropane trimethacrylate) polyfunctional monomer and 5.84% filler (zinc oxide, stearic acid, polyethylene glycol and antioxidant). The rubber samples designed for different vulcanization methods were obtained from raw rubber mixtures, as compressed sheets of 2 mm in the polyethylene foils to minimize oxidation. For EB and EB + MW treatments the sheets were cut in rectangular shape 0.15 x 0.15 m2. The physical properties of samples obtained by CV-BP EV-Vand EB + MW-V methods were evaluated by measuring the tearing strength, residual elongation, elongation at break, tensile strength, 300% modulus, 100% modulus, elasticity and hardness. The obtained results demonstrate an improvement of rubber several properties obtained by EB and EB + MW processing as compared to classical procedure using benzoyl peroxide.

Vaccine preparation by radiation processing.

A new radiation biotechnology for the acquirement of a commercial vaccine, designed for prophylaxis of ruminant infectious pododermatitis (IP), produced by gram negative bacteria Fusobacterium necrophorum (F.n.), is presented. Two different processes for preparing F.n. vaccine are used: a) the inactivation of F.n. bacteria exotoxins by microwave (MW) or/and electron beams (EB) irradiation; b) the isolation of exotoxins from F.n. cultures irradiated with MW or/and EB and the inactivation of isolated F.n. exotoxins with formalin. The EB irradiation of F.n. cultures produced simultaneously with the cells viability decrease an increasing of exotoxin quantity released in the culture supranatant as compared with classical methods. The MW irradiation is able to reduce the cells viability to zero but without an increase of exotoxin quantity in cultures supranatant. Instead of this MW irradiation, for certain conditions, is able to induce an important stimulation degree of the F.n. proliferation in cultures, from two to three log10. Two vaccine types were prepared: A1 vaccine that contains whole cell culture irradiated with MW/EB and A2 vaccine that contains cell-free culture supernatant of an MW/EB irradiated F.n. strain producing exotoxins. Also, other two vaccines are prepared: B1 and B2 that contain the same materials as A1 and A2 respectively, but without using MW/EB exposure. The vaccine efficiency is tested in ruminant farms in which IP evolves. It is expected that this new vaccine to offer a better protection, more than 60%, which is the best presently obtained result in ruminant farms.

SO2 and NOx removal by microwave and electron beam processing.

This work presents a method and a semi-pilot scale installation (SPSI) for the simultaneous SO2 and NOx removal by separate and combined microwave (MW) and electron beam (EB) irradiation. The SPSI consists mainly of the following units: a gaseous mixture preparation system (GMPS), a microwave source (MS) of 2.45 GHz and 4.2 kW maximum output power an electron beam source (EBS) of 1.8 MeVand 10.8 kW maximum output power and a multimode rectangular cavity (MRC), used as reaction chamber in which are injected both MW and EB fields. The most important parameters for high SO2 removal efficiencies obtained by MW technology are water and ammonia concentration, the gaseous mixture temperature during irradiation process and MW power level. The most important parameter for high NOx removal efficiency obtained by MW technology is MW power level. The removal efficiencies obtained by MW processing were up to 95% for SO2 and up to 55% for NOx. The additional use of EB irradiation to MW exposure strongly increases NOx removal efficiencies in comparison with MW exposure only, up to 95%, simultaneously providing very high values for the SO2 removal efficiency, near 100%.

Combined microwave and electron beam exposure facilities for medical studies and applications.

The paper presents two radiation exposure facilities (REFs) which permit separate and simultaneous irradiation with microwaves (MW) of 2.45 GHz and electron beams (EB) of 6.23 MeV for malignant melanoma (MM) cell investigations, in vitro (MW+EB-REF-vitro) and in vivo (MW+EB-REF-vivo). The REFs are specifically designed for the following medical studies: 1) The effects of separate and combined (successive and simultaneous) MW and EB irradiation on the B16F10 mouse--MM cell cultures without/with drugs incubation, 2) The effects of separate and combined MW and EB irradiation on human blood components irradiated in samples of integral blood from healthy donors and from donors with MM; 3) The effects of separate and combined MW and EB whole body irradiation on the C57 BL/6 mice bearing MM without/with drugs administration. Several representative results obtained by experiments with REFs in vitro and in vivo are discussed. The most important conclusion of the experimental results is that low dose-total body MW+EB irradiation combined with drugs administration could present a valuable potential for an advanced study in malignant melanoma therapy.

Cell investigations simultaneously with exposure to 2.45 GHz microwaves.

The paper presents two microwave (MW) exposure systems (MWESs) that permit observations and measurements on cell cultures during their exposure to MW of 2.45 GHz: MWES-1 and MWES-2. MWES-1 is designed for the measurement of the cell membrane fluorescence anisotropies (MFA) simultaneously with MW exposure. MWES-2 is designed for the cells culture exploration under an inverted microscope before, during and after MW exposure. MWES-1 consists mainly of a 2.45 GHz microwave generator (MWG-2.45 GHz-SAIREM) of 0-25 W, equipped with forward power and reflected power displaying, and an adjustable coaxial antenna immersed directly into the cuvette with the cells-suspension of a Spex type spectrofluorometer. The MW effect on membrane fluidity of B16F10 malignant melanoma (B16F10-MM) cells in suspension were investigated with MWES-1, by MFA measurements. We observed a MW induced transition temperature (ITT) rising strongly during the MW exposure as compared with ITT obtained by classical heating (CH). The MWES-2 consists of the MWG-2.45 GHz-SAIREM generator and a rectangular waveguide applicator with traveling wave placed between the condenser and the objective of a Zeiss Axiovert 200 microscope, equipped with a fluorescence device and image acquisition. The MW effects on shape and apoptosis of the B16F10-MM cells were investigate with MWES-2. The B16F10-MM cells exhibited visible shape changes during MW exposure up to 37 degrees C. The MW exposure induced cells apoptosis/necrosis in several seconds after that MW are applied, beginning with SAR = 1.5 W/sample, compared to CH controls exposed at the same temperature dynamics.

New Type of Sodium Alginate-g-acrylamide Polyelectrolyte Obtained by Electron Beam Irradiation: Characterization and Study of Flocculation Efficacy and Heavy Metal Removal Capacity.

The goals of the paper were first the obtainment and characterization of sodium alginate-g-acrylamide polyelectrolytes by electron beam irradiation in the range of 0.5 to 2 kGy, and second, the evaluation of flocculation efficacy and heavy metal removal capacity from aqueous solutions of known concentrations. Based on sodium alginate concentration, two types of grafted polymers were obtained. Physical, chemical, and structural investigations were performed. Flocculation studies under different stirring conditions on 0.5, 0.1 and 0.2% kaolin suspension were done. The removal capacity of Cu2+ and Cr6+ ions was also investigated. The acrylamide grafting ratio on sodium alginate backbone was found up to 2000% for samples containing 1% sodium alginate and up to 500% for samples containing 2% sodium alginate. Transmittances between 98 and 100% were obtained using, in the flocculation studies, polyelectrolytes containing 2% sodium alginate in concentrations of 0.5 and 1 ppm on kaolin suspension of 0.1 wt %. The polymer concentration was found critical for kaolin suspension of 0.05 and 0.1 wt %. Polymers containing 1% sodium alginate were efficient in Cr6+ ion removal, while those containing 2% in Cu2+ ion removal.

Hydrogels Synthesized by Electron Beam Irradiation for Heavy Metal Adsorption.

Poly(acrylamide co-acrylic acid) hydrogels were prepared by free-radical copolymerization of acrylamide and acrylic acid in aqueous solutions using electron beam irradiation in the dose range of 2.5 kGy to 6 kGy in atmospheric conditions and at room temperature. The influence of the absorbed dose, the amount of cross-linker (trimethylolpropane trimethacrylate) and initiator (potassium persulfate) on the swelling properties and the diffusion coefficient and network parameters of hydrogels were investigated. The structure and morphology of hydrogels were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The use of the obtained hydrogels by the removal of Cu2+ and Cr6+ from aqueous solutions was investigated at room temperature. During the adsorption of metal ions on hydrogels, the residual metal ion concentration in the solution was measured by an atomic absorption spectrophotometer (AAS). It has been established that the use of a relatively small amount of trimethylolpropane trimethacrylate for hydrogel preparation has led to the increasing of swelling up to 8500%.

Wood Sawdust/Natural Rubber Ecocomposites Cross-Linked by Electron Beam Irradiation.

The obtaining and characterization of some polymeric eco-composites based on wood sawdust and natural rubber is presented. The natural rubber was cross-linked using the electron beam irradiation. The irradiation doses were of 75, 150, 300 and 600 kGy and the concentrations of wood sawdust were of 10 and 20 phr, respectively. As a result of wood sawdust adding, the physical and mechanical properties such as hardness, modulus at 100% elongation and tensile strength, showed significant improvements. The presence of wood sawdust fibers has a reinforcing effect on natural rubber, similar or better than of mineral fillers. An increase in the irradiation dose leads to the increasing of cross-link density, which is reflected in the improvement of hardness, modulus at 100% elongation and tensile strength of blends. The cross-linking rates, appreciated using the Flory-Rehner equation, have increased with the amount of wood sawdust in blends and with the irradiation dose. Even if the gel fraction values have varied irregularly with the amount of wood sawdust and irradiation dose it was over 90% for all blends, except for the samples without wood sawdust irradiated with 75 kGy. The water uptake increased with increasing of fiber content and decreased with the irradiation dose.

Whole body microwave irradiation for improved dacarbazine therapeutical action in cutaneous melanoma mouse model.

A cutaneous melanoma mouse model was used to test the efficacy of a new therapeutical approach that uses low doses of cytostatics in conjunction with mild whole body microwave exposure of 2.45 GHz in order to enhance cytostatics antitumoral effect. Materials and Methods. A microwave exposure system for C57BL/6 mouse whole body microwave irradiation was designed; groups of 40 mice (males and females) bearing experimental tumours were subjected to a combined therapy comprising low doses of dacarbazine in combination with mild whole body irradiation. Clinical parameters and serum cytokine testing using xMAP technology were performed. Results. The group that was subjected to combined therapy, microwave and cytostatic, had the best clinical evolution in terms of overall survival, tumour volume, and metastatic potential. At day 14 the untreated group had 100% mortality, while in the combined therapy group 40% of mice were surviving. Quantifying serum IL-1 ß , IL-6, IL-10, IL-12 (p70), IFN- γ , GM-CSF, TNF- α , MIP-1 α , MCP-1, and KC during tumorigenesis and therapy found that the combined experimental therapy decreases all the inflammatory cytokines, except chemokine MCP-1 that was found increased, suggesting an increase of the anti-tumoral immune response triggered by the combined therapy. The overall metastatic process is decreased in the combined therapy group.