Sodium Alginate-g-acrylamide/acrylic Acid Hydrogels Obtained by Electron Beam Irradiation for Soil Conditioning.

Being both a cause and a victim of water scarcity and nutrient deficiency, agriculture as a sustainable livelihood is dependent now on finding new suport solutions. Biodegradable hydrogels usage as soil conditioners may be one of the most effective solutions for irrigation efficiency improvement, reducing the quantity of soluble fertilizers per crop cycle and combating pathogens, due to their versatility assured by both obtaining method and properties. The first goal of the work was the obtaining by electron beam irradiation and characterization of some Sodium Alginate-g-acrylamide/acrylic Acid hydrogels, the second one being the investigation of their potential use as a soil conditioner by successive experiments of absorption and release of two different aqueous nutrient solutions. Alginate-g-acrylamide/acrylic Acid hydrogels were obtained by electron beam irradiation using the linear accelerator ALID 7 at 5.5 MeV at the irradiation doses of 5 and 6 kGy. For this were prepared monomeric solutions that contained 1 and 2% sodium alginate, acrylamide and acrylic acid in ratios of 1:1 and 1.5:1, respectively, for the obtaining of materials with hybrid properties derived from natural and synthetic components. Physical, chemical, structural and morphological characteristics of the obtained hydrogels were investigated by specific analysis using swelling, diffusion and network studies and Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Four successive absorption and release experiments of some synthetic and natural aqueous solutions with nutrients were performed.

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.

Degradation Studies Realized on Natural Rubber and Plasticized Potato Starch Based Eco-Composites Obtained by Peroxide Cross-Linking.

The obtaining and characterization of some environmental-friendly composites that are based on natural rubber and plasticized starch, as filler, are presented. These were obtained by peroxide cross-linking in the presence of a polyfunctional monomer used here as cross-linking co-agent, trimethylolpropane trimethacrylate. The influence of plasticized starch amount on the composites physical and mechanical characteristics, gel fraction and cross-link density, water uptake, structure and morphology before and after accelerated (thermal) degradation, and natural (for one year in temperate climate) ageing, was studied. Differences of two orders of magnitude between the degradation/aging methods were registered in the case of some mechanical characteristics, by increasing the plasticized starch amount. The cross-link density, water uptake and mass loss were also significant affected by the plasticized starch amount increasing and exposing for one year to natural ageing in temperate climate. Based on the results of Fourier Transform Infrared Spectroscopy (FTIR) and cross-link density measurements, reaction mechanisms attributed to degradation induced by accelerated and natural ageing were done. SEM micrographs have confirmed in addition that by incorporating a quantity of hydrophilic starch amount over 20 phr and by exposing the composites to natural ageing, and then degradability can be enhanced by comparing with thermal degradation.

New green polymeric composites based on hemp and natural rubber processed by electron beam irradiation.

A new polymeric composite based on natural rubber reinforced with hemp has been processed by electron beam irradiation and characterized by several methods. The mechanical characteristics: gel fraction, crosslink density, water uptake, swelling parameters, and FTIR of natural rubber/hemp fiber composites have been investigated as a function of the hemp content and absorbed dose. Physical and mechanical properties present a significant improvement as a result of adding hemp fibres in blends. Our experiments showed that the hemp fibers have a reinforcing effect on natural rubber similar to mineral fillers (chalk, carbon black, silica). The crosslinking rates of samples, measured using the Flory-Rehner equation, increase as a result of the amount of hemp in blends and the electron beam irradiation dose increasing. The swelling parameters of samples significantly depend on the amount of hemp in blends, because the latter have hydrophilic characteristics.

Poly(acrylic acid)-Sodium Alginate Superabsorbent Hydrogels Synthesized by Electron-Beam Irradiation-Part II: Swelling Kinetics and Absorption Behavior in Various Swelling Media.

Hybrid hydrogels with superabsorbent properties based on acrylic acid (20%), sodium alginate (0.5%) and poly(ethylene oxide) (0.1%) were obtained by electron-beam irradiation between 5 and 20 kGy, and are characterized by different physical and chemical methods; the first results reported showed gel fractions over 87%, cross-link densities under 9.9 × 103 mol/cm3 and swelling degrees of 400 g/g. Two types of hydrogels (without and with 0.1% initiator potassium persulfate) have been subjected to swelling and deswelling experiments in different swelling media with different pHs, chosen in accordance with the purpose for which these superabsorbent materials were obtained, i.e., water and nutrients carriers for agricultural purposes: 6.05 (distilled water), 7.66 (tap water), 5.40 (synthetic nutrient solution) and 7.45 (organic nutrient solution). Swelling kinetics and swelling dynamics have been also studied in order to investigate the influence of swelling media type and pH on the absorption phenomenon. The swelling and deswelling behaviors were influenced by the hydrogel characteristics and pH of the swelling media. Both the polymeric chain relaxation (non-Fickian diffusion) and macromolecular relaxation (super case II) phenomenon were highlighted as a function of swelling media type.

The Influence of the Structural Architecture on the Swelling Kinetics and the Network Behavior of Sodium-Alginate-Based Hydrogels Cross-Linked with Ionizing Radiation.

The present work discusses the influence of the structural architecture of sodium alginate-co-acrylic acid-poly(ethylene) oxide hydrogels, crosslinked through electron beam (e-beam) radiation processing. The most important properties of the hydrogels were studied in detail to identify a correlation between the architecture of the hydrogels and their properties. Furthermore, the effect of sodium alginate (NaAlg) concentration, the amounts of the polymer blend, and the size of the samples on hydrogel properties were investigated. The results show that the hydrogels cross-linked (0.5% and 1% NaAlg) with 12.5 kGy exhibit improved physicochemical properties. High gel fraction levels (exceeding 83.5-93.7%) were achieved. Smaller hydrogel diameter (7 mm) contributed to a maximum swelling rate and degree of 20.440%. The hydrogel network was dependent on the hydrogels' diameter and the amount of polymer blend used. The hydrogels best suited the first-order rate constants and exhibited a non-Fickian diffusion character with diffusion exponent values greater than 0.5. This study indicates that the cross-linked hydrogel has good properties, particularly because of its high degree of swelling and extensive stability (more than 180 h) in water. These findings show that hydrogels can be effectively applied to the purification of water contaminated with metals, dyes, or even pharmaceuticals, as well as materials with a gradual release of bioactive chemicals and water retention.

NaAlg-g-AA Hydrogels: Candidates in Sustainable Agriculture Applications.

Nowadays, the degradation of agricultural soil due to various factors should be a major concern for everyone. In this study, a new sodium alginate-g-acrylic acid-based hydrogel was developed simultaneously by cross-linking and grafting with accelerated electrons to be used as soil remediation. The effect of irradiation dose and NaAlg contents on the gel fraction, network and structural parameters, sol-gel analysis, swelling power, and swelling kinetics of NaAlg-g-AA hydrogels have been investigated. It was demonstrated that NaAlg hydrogels show significative swelling power that is greatly dependent on their composition and irradiation dose; they keep the structure and are not degraded in different pH conditions and different water sources. Diffusion data revealed a non-Fickian transport mechanism (0.61-0.99) also specific to cross-linked hydrogels. The prepared hydrogels were proved as excellent candidates in sustainable agriculture applications.

Degradation by Electron Beam Irradiation of Some Elastomeric Composites Sulphur Vulcanized.

Composites based on natural rubber and plasticized starch obtained by the conventional method of sulfur cross-linking using four types of vulcanization accelerators (Diphenyl guanidine, 2-Mercaptobenzothiazole, N-Cyclohexyl-2-benzothiazole sulfenamide, and Tetramethylthiuram disulfide) were irradiated with an electron beam in the dose range of 150 and 450 kGy for the purpose of degradation. The vulcanization accelerators were used in different percentages and combinations, resulting in four mixtures with different potential during the cross-linking process (synergistic, activator, or additive). The resulting composites were investigated before and after irradiation in order to establish a connection between the type of accelerator mixture, irradiation dose, and composite properties (gel fraction, cross-linking degree, water absorption, mass loss in water and toluene, mechanical properties, and structural and morphological properties). The results showed that the mixtures became sensitive at the irradiation dose of 300 kGy and at the irradiation dose of 450 kGy, and the consequences of the degradation processes were discussed.

Poly(Acrylic Acid)-Sodium Alginate Superabsorbent Hydrogels Synthesized by Electron Beam Irradiation Part I: Impact of Initiator Concentration and Irradiation Dose on Structure, Network Parameters and Swelling Properties.

In the present paper, hydrogels based on acrylic acid (20%), sodium alginate (0.5%) and poly(ethylene oxide) (0.1%) were obtained by electron beam irradiation at room temperature with doses between 5 and 20 kGy, using potassium persulfate in concentrations up to 0.3% as a reaction initiator. The influence of initiator concentration and irradiation dose on hydrogel network parameters, swelling and deswelling behavior, gelation and degradation points, structure and morphology were investigated. Cross-link density increased with the irradiation dose and initiator addition, except at 20 kGy. The gel fraction was over 87.0% in all cases. Swelling experiments in distilled water showed swelling degrees of 40,000% at an irradiation dose of 5 kGy when a concentration of 0.1% initiator was added. A relationship between the swelling degree and irradiation dose, cross-linking degree (that increases from 0.044 × 102 to 0.995 × 102 mol/cm3) and mesh size (that decreases from about 220 nm to 26 nm) was observed. The addition of only 0.1% of PP led to the obtaining of hydrogels with a swelling degree of 42,954% (about 430 g/g) at an irradiation dose of 5 kGy and of 7206% (about 62 g/g) at 20 kGy, which are higher percentages than those obtained in the same irradiation conditions but without PP.

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.

New Materials Based on Ethylene Propylene DieneTerpolymerand Hemp Fibers Obtained by Green Reactive Processing.

The paper presents the obtaining of new green polymeric composites using a sustainable reactive processing method, namely electron beam irradiation. EPDM rubber mixtures were reinforced with different amounts of short hemp fibers, which were then irradiated at doses between 75 and 600 kGy. The samples were analyzed by determination of physical-mechanical properties, sol-gel analysis, crosslink density (using the well-known modified Flory-Rehner equation for tetra functional networks), determination of rubber-fiber interactions (using the Kraus equation), water uptake test and FTIR analysis. The obtained results indicate an improvement of the hardness, the tensile and tear strength as the quantity of hemp fibers increases. As the irradiation dose increases, there is an increase in the degree of crosslinking and the gel fraction. Analyzing the behavior of the irradiation samples using the Charlesby-Pinner equation, it is observed that all the samples tend to crosslink by irradiation, the share of degradation reactions being low. For these reasons, the new materials can be used in the food, pharmaceutical or medical field, because the obtained products are sterile and can be easily resterilized by irradiation. They have high elasticity values and can be used to make packaging, seals and other consumer goods.

Radiation Processing and Characterization of Some Ethylene-propylene-diene Terpolymer/Butyl (Halobutyl) Rubber/Nanosilica Composites.

Composites based on ethylene-propylene-diene terpolymer (EPDM), butyl/halobutyl rubber and nanosilica were prepared by melt mixing and subjected to different doses of electron beam irradiation. The effect of irradiation dose on the mechanical properties, morphology, glass transition temperature, thermal stability and water uptake was investigated. The efficiency of the crosslinking by electron beam irradiation was analyzed by Charlesby-Pinner parameter evaluation and crosslink density measurements. The scanning electron microscopy data showed a good dispersion of nanosilica in the rubber matrix. An improvement in hardness and 100% modulus was revealed by increasing irradiation dose up to 150 kGy. The interaction between polymer matrix and nanosilica was analyzed using the Kraus equation. Additionally, these results indicated that the mechanical properties, surface characteristics, and water uptake were dependent on crosslink characteristics.

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.

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.