Radiation grafting of ionically crosslinked alginate/chitosan beads with acrylic acid for lead sorption

Radiation-induced grafting of acrylic acid onto alginate/chitosan beads was performed in solution at a dose rate of 20.6 Gy/min of Co-60 gamma rays. The effect of absorbed dose on grafting yield was investigated. The characterization of the grafted and un-grafted beads was performed by FTIR spectroscopy and the swelling measurements at different pHs was studied. It is found that as the pH value increases the swelling degree increases up to pH 6 but with further increase in pH value the swelling decreases. Also, it is noticed that the grafting yield increased with increase the irradiation dose. Both un-grafted and grafted alginate/chitosan beads were examined as sorbents for the removal of Pb ions from aqueous solutions. The sorption behavior of the sorbents was examined through pH, and equilibrium measurements. Grafted alginate/chitosan beads presented higher sorption capacity for Pb ions than un-grafted beads.     

Surface modification of polymers. I. Vapour phase photografting with acrylic acid

Surfaces of low density polyethylene, high density polyethylene, and polystyrene have been modified by grafting with acrylic acid. Benzophenone and acrylic acid in the vapor phase were UV-irradiated in the presence of a polymer substrate. Grafting with acrylic acid took place in a thin layer on the surface, thus increasing the wettability of the polymer. After 5 min of irradiation, the contact angle against water had decreased to 20° for polystyrene and 50° for the polyethylene samples. ESCA measurements on samples irradiated for 5 min showed a 90% poly(acrylic acid) coverage of the surface for polystyrene, 63% for low density polyethylene, and 56% for high density polyethylene. Acetone or ethanol were used as carriers of monomer and initiator. Acetone was able to initiate grafting and was found to promote and direct grafting to the surface. The stability of the acrylic acid grafted surfaces was studied by contact angle measurements and ESCA. At room temperature, the grafted layer is confined to the surface, but when the material was heated in air the surface was reshaped into a hydrophobic one. The process was reversible. In aqueous surroundings at elevated temperatures the hydrophilic character of the surface was restored.     

Modification of polypropylene fibres by preirradiation technique

The modification of polypropylene fibres (POP) and POP fleece prepared by preirradiation technique is discussed. Grafting measure, hydrophility change and dyeing ability of the radiation modified samples were studied. The preirradiation and the simultaneous one were performed in a chamber type RCH-gamma-30 radiation equipment, having the emitters charge of⁶⁰Co. For radiation-induced grafting 5–30% acrylic acid solution was used. It was proved that the percentage of irradiation-induced grafting of both POP fibres and POP fleece increased with an increase in the radiation dose and the concentration of acrylic acid. Samples modified by this technique have a good dyeing ability and their dyeing intensity increased parallel with the percentage of grafting.     

Studies on the graft copolymerization of cellulosic materials

Graft copolymers of acrylic acid on cellulosic materials were obtained by use of ceric ion in aqueous medium at various temperatures. The level of incorporation of poly(acrylic acid) grafts and the efficiency of grafting were significantly reduced as the temperature of polymerization was increased from 35° to 60°C. The uptake of cadmium and copperions from aqueous solution by the cellulose-g-poly(acrylic acid) copolymer was examined by equilibrium and dynamic sorption studies. The amount of metal ions removed from solution depended on the metal ion type, initial concentration of the metal ion solution, level of incorporation of poly(acrylic acid) in the graft copolymer and the temperature of the metal ion solution.     

Effect of chemical quenching on background counting rate in tritium channel of a large volume liquid scintillation counter

Background counting rate in tritium channel of a large volume liquid scintillation counter increased with water content ranged 0 to 50% of liquid scintillator. This phenomenon can be explained as follows: The height of scintillation pulses of Compton electrons induced by background gamma radiation is lowered by chemical quenching and shifts to tritium channel. The background counting rate in tritium channel showed a linear relationship with external standard channel ratio of background samples. This relationship is applicable to determine the correct background counting rate for quenching samples and to achieve higher precision of tritium measurement.     

The effect of concentration of acrylic acid,dose rates and temperature on preirradiated graft of natural rubber-based thermoplastic elastomer

Grafting acrylic acid (AAc) onto thermoplastic elastomer (TE) films, a kind of product from natural rubber latex block-grafted by methyl methacrylate monomer was investigated. The preirradiated dose from a gamma Co-60 source for TE at 75 kGy was considered to be useful. Significant concentration of AAc aqueous solution for the grafting process is 20% (vol%). Dose rate of about 3.4 kGy/h is more effective for the graft. The temperature of around 90°C is suitable for obtaining a higher degree of graft. It is observed that the rate of grafting of AAc onto TE is proportional to 0.48 power of dose rate and 1.9 power of AAc concentration. The rate of grafting can be expressed as R_g=k·I^0.48·M^1.9. On the other hand, overall activation energy of the graft is estimated about 7.2 Kcal/mol. The FTIR spectrum analysis of TE and TE-g-AAc films was proceeded.     

Grafting polymerization of acrylic acid onto preirradiated polypropylene fabric

Acrylic acid (AAc) was grafted onto polypropylene (PP) fabric by a preirradiation method using a Co-60 gamma ray. The effect of absorbed dose, AAc concentration, reaction temperature, reaction time, storage time, as well as the effect of ferrous ion and sulfuric acid on the degree of grafting were determined. It has been shown that the synergistic effect of sulfuric acid with the ferrous sulfate can not only increase the grafting yield, but also decrease the apparent activation energy for the grafting. It leads to the possibility of getting a particular grafting yield at a lower absorbed dose. In this experiment, It has also been shown that the grafting activity of preirradiated PP fabric in AAc aqueous solution could be well kept at room temperature for a long period.     

Novel comb-type hydrogels of net-[PP-g-AAc]-g-4VP synthesized by gamma radiation,with possible application on Cu2+ immobilization

A novel comb-type grafted hydrogel system of net-[PP-g-AAc]-g-4VP was synthesized by gamma radiation in three steps. In the first step a pH sensitive graft copolymer of AAc onto PP film was obtained by radiation grafting of acrylic acid (AAc) onto polypropylene (PP) films in aqueous solution at radiation doses of 10 kGy with a ⁶⁰Co source. The grafted side chains of poly (acrylic acid) (PAAc) were then cross-linked with gamma radiation at different radiation doses to give net-[PP-g-AAc]. Finally, 4-vinylpyridine (4VP) was grafted into the net-[PP-g-AAc]. The comb-type grafted hydrogel obtained, net-[PP-g-AAc]-g-4VP, has been studied through determination of graft yield and swelling behavior at room temperature. Two critical pH values were found for net-[PP-g-AAc]-g-4VP at 4.5 and 7.2. Initial studies on the immobilization of Cu²⁺ ions from solution into net-[PP-g-AAc]-g-4VP films were performed.The comb-type grafted hydrogel, grafted onto PP was also characterized by differential scanning calorimetry (DSC), scanning electronic microscopy (SEM) and FTIR-ATR.     

Swelling characteristics of konjac glucomannan superabsobent synthesized by radiation-induced graft copolymerization

Graft copolymerization of konjac glucomannan (KGM) and acrylic acid was induced by ⁶⁰Co-γ irradiation at room temperature. The effects of radiation dose and monomer-to-KGM ratio on grafting yield and equilibrium water absorbency were investigated. The KGM-based superabsorbent polymer (KSAP) could absorb water 625 times of its dry weight when the radiation dose was 5.0 kGy and monomer-to-KGM ratio was 5. The structure of KSAP was characterized by FTIR, XRD, and SEM. KSAP showed a lower crystallinity than KGM. The porous microstructure of KSAP was revealed by SEM. The diffusion mechanism of water in the hydrogel is consistent with the anomalous diffusion model. Cations, especially multivalent cations, greatly reduced water absorbency of KSAP. Rising temperature, acidic or basic solutions are not favorable for the swelling of KSAP.     

Gamma radiation synthesis of comb-type graft hydrogels based on poly(acrylic acid) and 4-vinylpyridine

A pH-sensitive comb-type hydrogel was obtained by gamma radiation polymerization and crosslinking of acrylic acid (AAc) in solution. The pH-sensitive 4-vinylpyridine (4VP) was then grafted to the poly acrylic acid (PAAc) hydrogel using gamma radiation from a ⁶⁰Co source. The comb type graft polymers obtained (net-PAAc)-g-4VP has been studied through determination of graft yield and swelling behavior. The critical pH value was found to be 5.6. The apparent mechanical properties appear to be qualitatively better than hydrogels of PAAc upon swelling. The new comb-type system presents faster swelling response (30 h) than the polyacrylic acid hydrogel (50 h). The increase in dose rate from 7.3 to 11.3 kGy h⁻¹, increase the radiation grafting percentage of 4VP in the system. Comb-type polymers were also characterized by DSC, TGA and FTIR-ATR.     

Photoinitiated grafting polymerization of acrylic acid onto the surface of polyethylene under pulsed laser radiation

Photoinduced grafting polymerization on the surface of PE films induced by nanosecond pulsed laser radiation is studied. The grafting is performed from the liquid phase composed of acrylic acid and a photoinitiator (benzophenone) dissolved in it. Pulsed laser radiation with a wavelength of 355 nm, a pulse duration of 11 ns, and a repetition rate of 10 Hz is used. Formation of the surface-graft polymer is followed by IR-ATR spectroscopy and contact-angle measurements. It is found that the time of laser treatment sufficient for the efficient modification of the PE surface with the grafted poly(acrylic acid) is in the range from 0.5 to 1.0 s at a laser-pulse energy density of 200–500 mJ/cm². At energy densities beyond this range, the efficiency of the reaction decreases rapidly. The results on laser grafting are compared with the results of grafting during UV irradiation with a lamp at a wavelength of 365 nm.     

Role of cations in radiation grafting and homopolymerization

The grafting of acrylic acid in aqueous solution to nylon 6 film has been studied in the presence of ferrous, ferric, and cupric salts. The mutual irradiation technique was adopted using a ⁶⁰Co source. The anions were found to have no effect on the grafting or homopolymerization, but both of these processes were suppressed by the cations in the following order of effectiveness: Cu²⁺ > Fe²⁺ > Fe³⁺. The rate constant for the capture of hydroxyl radicals by acrylic acid has been determined as 6 × 10⁹ 1. mole^?1 sec^?1 by pulse radiolysis using the CNS^? competition method. By invoking this result, mechanisms have been suggested for the process of chain termination by metal cations.     

Determination of (3)H and (85)Kr in aqueous samples by liquid scintillation techniques

Analytical procedures have been developed for the simultaneous determination of tritium and krypton-85 in aqueous solutions by liquid scintillation techniques. The effects of sample size, amount of water and dye were investigated.     

In vitro study of proteins surface activity by tritium probe

A new technique for in vitro studies of biomacromolecules interactions, their adsorption at aqueous/organic liquid interfaces and distribution in the bulk of liquid/liquid systems was developed. The method includes (1) tritium labeling of biomolecules by tritium thermal activation method and (2) scintillation phase step with organic phase, which can be concerned as a model of cellular membrane. Two globular proteins lysozyme and human serum albumin tested. We have determined the conditions of tritium labeling when labeled by-products can be easy separated by means of dialysis and size-exclusion chromatography. Scintillation phase experiments were conducted for three types of organic liquids. Thus, the influences of the nature of organic phase on proteins adsorption and its distribution in the bulk of aqueous/organic liquid system were determined. It was found that proteins possess high surface activity at aqueous/organic liquid interface. Furthermore, values of hydrophobicity of globular proteins were found by the experiment.     

Surface modification of polyolefins by photografting of acrylic monomers

High-speed surface modification of polypropylene (PP) and polyethylene (PE) films has been achieved by liquid phase photograft polymerisation of acrylic acid (AA) and hydroxypropyl acrylate (HPA). Benzophenone was used as photoinitiator to generate polymer radicals at the surface of the polyolefin film. The grafting reaction was carried out in aqueous solution or with the neat monomer, which was laminated between two PP films, in the presence of air. Under the intense illumination of a UV-curing line, acrylic acid was grafted within seconds to polypropylene films or fabrics, which were thus made hydrophilic. Direct evidence of surface grafting was obtained through infrared spectroscopy analysis and surface energy measurements. This continuous photografting process proved to be very efficient to improve the adhesion of UV-cured acrylate coatings on polyolefin-made materials.     

γ-Ray-induced grafting of DMAEMA and AAc onto PP by two step method

Binary graft copolymerization of thermosensitive 2-(dimethylamino) ethyl methacrylate (DMAEMA) and pH sensitive acrylic acid (AAc) monomers onto polypropylene (PP) films was carried out by a two step method using a ⁶⁰Co gamma radiation source. The PP film was initially modified by grafting of DMAEMA through a direct method. The DMAEMA-g-PP film obtained was then subjected to radiation grafting of AAc by the pre-irradiation method to give (DMAEMA-g-PP)-g-AAc. The optimal conditions, such as reaction time, reaction temperature, monomer concentration, and dose were studied. The grafted samples were verified by the FTIR-ATR spectroscopy and swelling; thermal properties were analyzed by DSC and TGA.     

Raft mediated surface grafting of t‐butyl acrylate onto an ethylene–propylene copolymer initiated by gamma radiation

RAFT mediated grafting of poly(t‐butyl acrylate) onto the surface of a commercial poly(ethylene‐co‐propylene), Elpro, has been carried out using initiation by ⁶⁰Co γ‐radiation at 298 and 273 K. The polymerizations were in bulk monomer and using the RAFT agent 1‐phenylethyl phenyldithioacetate. The rates of homopolymerization and grafting were found to decrease with increasing RAFT agent concentration, indicating that both polymerization processes involve participation of the RAFT agent. There was good agreement between the predicted and experimental molecular weights of the homopolymer that had a narrow polydispersity. The poly(t‐butyl acrylate) grafts were hydrolyzed by trifluoroacetic acid to form poly(acrylic acid) grafts, which could either be further functionalized or used to control the surface polarity of the Elpro. ATR‐FTIR spectroscopy was used to characterize the grafts and Raman spectroscopy was used to assess the depth of the grafts. The water contact angle for the Elpro surface grafted with poly(acrylic acid) was found to be linearly dependent on the amount of the graft present. The living nature of the grafted chains was demonstrated by the addition of a second block of polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1074–1083, 2007     

Preparation of ion-exchange fiber from polypropylene waste with grafted polyacrylic acid

A procedure was developed for preparing weakly acidic cation exchanger from polypropylene fiber wastes by grafting of acrylic acid to the preoxidized surface of the fiber in an aqueous solution.     

A radioanalytical technique to study the behavior of organic toxicants applied to a study of the photodegradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin

A general method for tritium labeling of organic compounds by the use of thermal activation of tritium is described. It allows obtaining uniformly tritium-labeled organic compounds with high specific activity (up to 50 Ci/mmol) which permits tracing the majority of the biodegradation products of compounds studied. More than 40 compounds were labeled using this simple, rapid and inexpensive method. Separation of the biodegradation products is performed by thin layer chromatography. Quantification is performed by direct measurement of the radioactivity by liquid scintillation counting after transfer of the layer from TLC plates into scintillation vials, or by densitometry of autoradiographs. The technique is useful for a wide range of organic compounds, including ones with unknown structure, and can be applied to various in vivo and in vitro studies.     

Photoinduced grafting polymerization onto the surface with the use of radiation of high-power ultraviolet light-emitting diodes

The photoinduced grafting polymerization of acrylic acid onto the surface of a polypropylene film under the action of radiation with a wavelength of 365 nm and an intensity of 8–193 mW/cm² emitted by high-power UV light-emitting diodes is studied. Grafting is performed from a thin layer of the aqueous solution of the monomer onto the surface containing a photoinitiator (benzophenone) deposited from a solution in a volatile solvent. The amount of graft polymer is determined with the use of ATR FTIR spectroscopy. At an intensity of UV radiation of 193 mW/cm², the time of attainment of grafting-polymerization saturation is decreased by a factor of 6 relative to this time at an intensity of 8 mW/cm², typical for emitters based on mercury lamps. The rate of grafting polymerization in the studied UV-radiation-intensity range grows in proportion to the square root of intensity.