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.

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.

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.

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.

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.

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.

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 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.

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.

Effects of Electron Beam Irradiation on the Mechanical, Thermal, and Surface Properties of Some EPDM/Butyl Rubber Composites.

The effects of electron beam irradiation on the properties of ethylene propylene diene monomer (EPDM)/butyl rubber composites in presence of a polyfunctional monomer were investigated by means of differential scanning calorimetry (DSC), thermal analysis, scanning electron microscopy (SEM), attenuated total reflection absorption infrared spectroscopy (ATR-IR), and mechanical and surface energy measurements. The samples were exposed over a wide range of irradiation doses (20⁻150 kGy). The EPDM matrix was modified with butyl rubber, chlorobutyl rubber, and bromobutyl rubber. The gel content and crosslink density were found to increase with the electron beam irradiation dose. The values of the hardness and modulus increased gradually with the irradiation dose, while the tensile strength and elongation at break decreased with increasing irradiation dose. The EPDM/butyl rubber composites presented a higher thermal stability compared to the initial EPDM sample. The incorporation of butyl rubbers into the EPDM matrix led to an increase in material hydrophobicity. A similar trend was observed when the irradiation dose increased. The greatest change in the surface free energy and the contact angles occurs at an irradiation dose of 20 kGy. The Charlesby⁻Pinner plots prove the tendency to crosslinking as the irradiation dose increases.

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%.

Development and Characterization of Polymer Eco-Composites Based on Natural Rubber Reinforced with Natural Fibers.

Natural rubber composites filled with short natural fibers (flax and sawdust) were prepared by blending procedure and the elastomer cross-linking was carried out using benzoyl peroxide. The microbial degradation of composites was carried out by incubating with Aspergillus niger recognized for the ability to grow and degrade a broad range of substrates. The extent of biodegradation was evaluated by weight loss and cross-linking degree study of composites after 2 months incubation in pure shake culture conditions. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) have proved to be precious and valuable instruments for morphological as well as structural characterization of the composites before and after incubation with Aspergillus niger.

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.

New Elastomeric Materials Based on Natural Rubber Obtained by Electron Beam Irradiation for Food and Pharmaceutical Use.

The efficiency of polyfunctional monomers as cross-linking co-agents on the chemical properties of natural rubber vulcanized by electron beam irradiation was studied. The following polyfunctional monomers were used: trimethylolpropane-trimethacrylate, zinc-diacrylate, ethylene glycol dimethacrylate, triallylcyanurate and triallylisocyanurate. The electron beam treatment was done using irradiation doses in the range of 75 kGy-300 kGy. The gel fraction, crosslink density and effects of different aqueous solutions, by absorption tests, have been investigated as a function of polyfunctional monomers type and absorbed dose. The samples gel fraction and crosslink density were determined on the basis of equilibrium solvent-swelling measurements by applying the modified Flory-Rehner equation for tetra functional networks. The absorption tests were done in accordance with the SR ISI 1817:2015 using distilled water, acetic acid (10%), sodium hydroxide (1%), ethylic alcohol (96%), physiological serum (sodium chloride 0.9%) and glucose (glucose monohydrate 10%). The samples structure and morphology were investigated by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy techniques.

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.

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.

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.