Rheological study of polypropylene irradiated with polyfunctional monomers

The aim of this paper is to investigate the rheological properties of polypropylene (PP) modified by ionization radiation (gamma rays) in the presence of two different monomers. The samples were mixed in a twin-screw extruder with ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TMPTMA) with concentration in the range of 0.5-5.0 mmol. After that, they were irradiated with 20 kGy dose of gamma radiation. The structural modification of polypropylene was analyzed in the melt state by measuring melt flow rate (MFR), η* (complex viscosity) and G′ (storage modulus) in the angular frequency range of 10⁻¹ to 3 × 10² rad s⁻¹. From the oscillatory rheology data, one could obtain the values of η₀ (zero shear viscosity) that would be related to the molar mass. All results were discussed with respect to the crosslinking and degradation process that occur in the post-reactor treatment to produce controlled rheology polypropylene.The resulting polymeric materials were submitted the cytotoxicity in vitro test by neutral red uptake methodology with NCTC L 929 cell line from American Type Culture Collection bank. All modified PP samples presented no cytotoxicity.     

IPN’s of acrylic acid and N-isopropylacrylamide by gamma and electron beam irradiation

Interpenetrating networks (IPN) of temperature sensitive N-isopropylacrylamide (NIPAAm) and pH sensitive acrylic acid (AAc) monomer were prepared in two consecutive steps. Hydrogels of AAc were synthesized by gamma radiation from a ⁶⁰Co gamma source and an electron beam from a Van de Graaff accelerator. A second hydrogel of NIPAAm was synthesized within the first AAc hydrogel by polymerization and cross-linking with a redox initiator and cross-linking agent. The thermal and pH sensitivity of the hydrogels were determined by measuring the swelling, and the morphology and composition by SEM.     

Drug release assays from new chitosan/pHEMA membranes obtained by gamma irradiation

With the purpose of obtaining a biocompatible and microbiologically safe matrix that simultaneously could be used as wound dressing material and as a controlled drug release system, membranes with different thickness and different contents in chitosan and hydroxyethyl methacrylate (HEMA) have been prepared by γ irradiation from a ⁶⁰Co source. Antibiotic release experiments were performed before or after irradiation over amoxicillin loaded chitosan/pHEMA membranes in physiological saline solution, and monitored by UV-Vis spectrometry.Results point out a fast amoxicillin release with similar release profile in all studied membranes. The amount of released drug was shown to be dependent on membranes network crosslinking due composition, radiation and membrane thickness.     

Radiation-induced grafting of N-isopropylacrylamide and acrylic acid onto polypropylene films by two step method

Binary graft copolymerization of pH sensitive acrylic acid (AAc) and thermosensitive N-isopropylacrylamide (NIPAAm) monomers onto pre-irradiated polypropylene films (PP) was carried out by two individual steps using a Co⁶⁰ gamma radiation source. The influence of preparation conditions, such as pre-irradiation dose and reaction time on grafting yield was studied. The swelling behavior and FTIR-ATR study for PP films grafted films were investigated.     

Modification of poly(ether ether ketone) by ion irradiation

Poly(ether ether ketone) was irradiated with 3.0 MeV Si²⁺, 3.25 MeV Cu²⁺ and 4.8 MeV Ag²⁺ ions to the fluences from 10¹² to 10¹⁴ cm⁻² and the effects of irradiation were studied using ERDA, RBS and FTIR methods. The irradiation leads to release of hydrogen from the PEEK surface layer modified by the ion beam. The release is mild for low ion fluences but it becomes more pronounced at the ion fluences above 10¹³ cm⁻². At highest ion fluences the hydrogen concentration falls to 20-35% of its initial value. In contrast to hydrogen no significant oxygen release was observed. The kinetic of the hydrogen release is similar for the three ion species. FTIR measurement shows deep structural changes of the polymer structure resulting from the ion irradiation.     

Beneficial effect of gamma irradiation on the N-deacetylation of chitin to form chitosan

The effect of gamma irradiation on the N-deacetylation of chitin to form chitosan was studied. Chitin from crab shells was irradiated up to 20 kGy and N-deacetylated in aqueous NaOH solution (40% and 60% w/w) at 60 and 100 °C for 60 min. The degree of N-deacetylation (DD) of non-irradiated and irradiated samples was determined by IR-band ratio method. It was found that higher extent of N-deacetylation was achieved for the chitin samples irradiated up to 20 kGy doses as compared to non-irradiated chitin. The DD values of chitin, prepared from non-irradiated and 20 kGy irradiated chitins by N-deacetylation at 60 °C with 40% NaOH for 60 min, were found to be 38% and 60%, respectively. The increase in DD by irradiation was interpreted as a result of reduction in molecular weight of chitin. Low dose irradiation of chitin has provided the possibility of its N-deacetylation into chitosan at much milder reaction conditions.     

Effect of gamma irradiation on the properties of tyre cords

Gamma irradiation of high tenacity Nylon 6.6 (Ny 66) and polyester (PET) tyre cords was investigated. The untreated and treated tyre cords with different twist levels were irradiated at different dose rates in air. The effects of irradiation on both Ny 66 and PET cords were not found to be depending on the twist levels of the cords. The changes in the mechanical and thermal properties with absorbed dose at two different dose rates were measured. The mechanical properties were observed to deteriorate with increasing dose for Ny 66 cords, whereas remained almost unchanged for PET cords both in greige and dipped forms. Hot shrinkage value for the greige Ny 66 cords was found to be improved, i.e. decreased. This decrease was much lower for greige PET than Ny 66 cords. It is concluded that PET cord has higher radiation resistance than Ny 66 cord and the effects of high energy irradiation on tyre cords have to be taken into consideration during tyre design if pre-vulcanization with high energy radiation is to be applied.     

Effects of electron beam irradiation on binary polyamide-6 blends with metallocene copolymers

The effect of electron beam irradiation on thermal and mechanical properties, and SEM morphology of polyamide-6 (PA-6) blends with grafted copolymers was investigated. High toughness materials were obtained with ethylene-polypropylene-diene grafted copolymers without significant variations in their thermal properties and Izod impact strength at room temperature and −30 °C with the irradiation doses used.     

10 MeV Au ion irradiation effects in an MgO-HfO2 ceramic-ceramic (CERCER) composite

Room temperature ion irradiation damage studies were performed on a ceramic composite intended to emulate a dispersion nuclear fuel. The composite is composed of 90-mole% MgO and 10-mole% HfO₂. The as-synthesized composite was found to consist of Mg₂Hf₅O₁₂ (and some residual HfO₂) particles embedded in an MgO matrix. X-ray diffraction revealed that nearly all of the initial HfO₂ reacted with some MgO to form Mg₂Hf₅O₁₂. Ion irradiations were performed using 10 MeV Au³⁺ ions at room temperature over a fluence range of 5 × 10¹⁶-5 × 10²⁰ Au/m². Irradiated samples were characterized using both grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM), the latter using both selected-area electron diffraction (SAED) and micro-diffraction (μD) on samples prepared in cross-sectional geometry. Both GIXRD and TEM electron diffraction measurements on a specimen irradiated to a fluence of 5 × 10²⁰ Au/cm², revealed that the initial rhombohedral Mg₂Hf₅O₁₂ phase was transformed into a cubic-Mg₂Hf₅O₁₂ phase. Finally, it is important to note that at the highest ion fluence used in this investigation (5 × 10²⁰ Au/m²), both the MgO matrix and the Mg₂Hf₅O₁₂ second phase remained crystalline.     

New separator prepared by electron beam irradiation for high voltage lithium secondary batteries

Grafted separators, for which poly(ethylene glycol) borate acrylate (PEGBA) was grafted onto polyethylene (PE) separator, were newly prepared by electron beam irradiation. The grafted separators were characterized by FT-IR, energy dispersive X-ray spectrometer (EDS). The morphological changes of the grafted separators were investigated by scanning electron microscopy (SEM). The degree of grafting was increased with irradiation doses. The ionic conductivity of the grafted separator showed the highest value of 6.24 × 10⁻⁴ S cm⁻¹ at 10 kGy. In addition, its lithium ion transference number and electrochemical stability were enhanced to 0.53 and 4.8 V, respectively owing to anion trapping effect of the grafted unit. The Li ion cells using the grafted separator showed better cycle performances than that using conventional PE separator at various C-rates and high voltage operation conditions. It is suggested that this grafted separator can be a promising candidate for high voltage operation of lithium secondary batteries.     

Properties of the acrylic acid polymers obtained by atmospheric pressure plasma polymerization

Plasma polymers of acrylic acid were obtained using an atmospheric pressure discharge system. The plasma polymerization reactor uses a dielectric barrier discharge, with the polyethylene terephthalate dielectric acting as substrate for deposition. The plasma was characterized by specific electrical measurements, monitoring the applied voltage and the discharge current. Based on the spatially resolved optical emission spectroscopy, we analyzed the distribution of the excited species in the discharge gap, specific plasma temperatures (vibrational and gas temperatures) being calculated with the Boltzmann plot method. The properties of the plasma polymer films were investigated by contact angle measurements, infrared and UV-Vis spectroscopy, scanning electron microscopy. The films produced by plasma polymerization at atmospheric pressure showed a hydrophilic character, in correlation with the strong absorbance of OH groups in the FTIR spectrum. Moreover, the surface of the plasma polymers at micrometric scale is smooth and free of defects without particular features.     

Static properties and moisture content properties of polyester fabrics modified by plasma treatment and chemical finishing

Low temperature plasma treatment has been conducted in textile industry and has some success in the dyeing and finishing processes. In this paper, an attempt was made to apply low temperature plasma treatment to improve the anti-static property of polyester fabric. The polyester fabrics were treated under different conditions using low temperature plasma. An Orthogonal Array Testing Strategy was employed to determine the optimum treatment condition. After low temperature plasma treatment, the polyester fabrics were evaluated with different characterisation methods. Under the observation of scanning electron microscope, the surface structure of low temperature plasma-treated polyester fabric was seriously altered. This provided more capacity for polyester to capture moisture and hence increase the dissipation of static charges. The relationship between moisture content and half-life decay time for static charges was studied and the results showed that the increment of moisture content would result in shortening the time for the dissipation of static charges. Moreover, there was a great improvement in the anti-static property of the low temperature plasma-treated polyester fabric after comparing with that of the polyester fabric treated with commercial anti-static finishing agent.     

Radiation synthesis of low swelling acrylamide based hydrogels and determination of average molecular weight between cross-links

A comparative analysis of determination of cross-link density (ν_e) of hydrogels by using swelling tests and mechanical measurements has been made. Poly(acrylamide/methacrylamide) P(AAm/MAAm) and poly(acrylamide/hydroxyethyl methacrylate) P(AAm/HEMA) hydrogels were prepared by using gamma rays and used as model hydrogel systems. The uniaxial compression test was applied to cylindrical gel samples in the swollen state at pH 7. Stress-strain curves of hydrogels were evaluated to calculate the shear modulus values. The average molecular weight between cross-links and ν_e obtained from mechanical measurements were significantly different than the values obtained from swelling experiments. Large differences were attributed to the uncertainty on the value of the χ parameter used in the Flory-Rehner equation. ±1% change in this parameter doubled or reduced the value of hydrogel to half value.     

DSC studies of retrogradation and amylose-lipid complex transition taking place in gamma irradiated wheat starch

The effect of gamma irradiation (⁶⁰Co) with doses of 5-30 kGy on the amylose-lipid complex transition and retrogradation occurring in gels containing ca. 50% and ca. 20% wheat starch was studied by differential scanning calorimetry (DSC) during heating-cooling-heating cycles (up to three cycles). Transition of the amylose-lipid complex occurs in all the irradiated samples at a lower temperature as compared to the non-irradiated starch. That effect was larger when the radiation dose was higher. A further thermal treatment causes a decrease of the transition temperature in the irradiated samples, with no effect or increase of that temperature observed for the non-irradiated ones. Irradiation hinders retrogradation taking place in 50% gels but facilitates the process occurring in 20% gels. The differences between the irradiated and the non-irradiated samples are more evident in the every next heating or cooling cycle as well as after storage and in the case of ca. 50% suspensions as compared to ca. 20% suspensions. The results point out to the deterioration of the structure of the complexes formed in the irradiated starch as compared to the non-irradiated one.     

Irradiation effects in an HfO2/MgO/HfO2 tri-layer structure induced by 10 MeV Au ions

In this report, we present radiation damage effects in a thin film, tri-layer structure, HfO₂/MgO/HfO₂. Irradiations were performed with 10 MeV Au ions in a recently developed medium energy ion irradiation facility at Los Alamos National Laboratory, which is described in this paper. Energy deposition by 10 MeV Au ions corresponds to a mixed regime, wherein electronic and nuclear stopping contribute to radiation damage. In this study, we investigated modifications of both surface and bulk properties in order to assess the structural stability of our oxide tri-layers under the severe irradiation conditions employed here. The most dramatic structural changes were observed to occur on the surfaces of the tri-layer samples. Surface features consisted of large craters and spires. The dimensions of these craters and spires exceed those of the individual ion tracks by almost three orders of magnitude. As for the bulk tri-layer structure, our conclusions are that this structure is stable in terms of: (i) resistance to amorphization; (ii) resistance to compositional mixing and (iii) resistance to pronounced nucleation and growth of extended defects. The main effect observed in the tri-layer structure was the transformation of the first HfO₂ layer from a monoclinic to either a tetragonal or cubic form of HfO₂.     

Preparation of polymer-coated separators using an electron beam irradiation

A polymer-coated polyethylene (PE) separator was prepared by a dip-coating of PVDF-HFP/PEGDMA on both sides of a PE separator followed by an electron beam irradiation. The thermal and electrochemical properties of the polymer-coated PE separator were investigated by using FT-IR, SEM, DSC and an impedance analyzer. The results showed that the coated PVDF-HFP/PEGDMA layer was covalently bound to the PE separator and also crosslinked by an electron beam irradiation. Thermal shrinkage dramatically decreased with an increase in the absorption dose and the PEGDMA content due to the crosslinking of the coated PVDF-HFP/PEGDMA by an irradiation. The PE separator coated with the composition of PVDF-HFP/PEGDMA (9.5/0.5) and irradiated to 150 kGy showed the highest electrolyte uptake of 125% and ionic conductivity of 3.82 × 10⁻⁴ S/cm at room temperature.     

TEM investigations of MN nitride phases in a 9% chromium ferritic/martensitic steel with normalization conditions for nuclear reactors

The investigations on the precipitate phases in a 9%Cr ferritic/martensitic steel under different normalization conditions have been made by using a transmission electron microscope and an energy-dispersive X-ray spectroscopy. Hot-rolled steel samples were normalized at 1050-1200 °C for 1-2 h followed by an air cooling to room temperature. MN vanadium nitride precipitates with a plate-like morphology and a chemical formula of about (V_0.4Nb_0.4Cr_0.2)N have been observed at triple junctions, grain boundaries and within matrix in the steel samples normalized at 1050-1150 °C for 1-2 h, but they were dissolved out at 1200 °C within 1 h. Vanadium nitride is a stable phase at 1050 °C according to thermocalc prediction of equilibrium phases in the steel. With increasing normalizing temperature and time, there was no a striking change in the chemical composition of metallic elements in the MN phase, but a considerable increase in the size of the MN precipitate.     

Preparation of a new micro-porous poly(methyl methacrylate)-grafted polyethylene separator for high performance Li secondary battery

In this study, micro-porous poly(methyl methacrylate)-grafted polyethylene separators (PE-g-PMMA) were prepared by a radiation-induced graft polymerization of methyl methacrylate onto a conventional PE separator followed by a phase inversion. After the phase inversion, the micro-pores were generated in the grafted PMMA layer. The prepared micro-porous PE-g-PMMA separators showed an improved electrolyte uptake and ionic conductivity due to their improved affinity with a liquid electrolyte and the presence of pores in the grafted PMMA layer. The PE-g-PMMA separators exhibited a lower thermal shrinkage compared to the original PE separator. The PE-g-PMMA separators showed a better oxidation stability up to 5.0 V when compared to the original PE separator (4.5 V).     

Study of H loss from hydrogenated Hg1−xCdxTe under high electronic excitation by elastic recoil detection analysis (ERDA)

Large erosion (∼1.1 × 10⁴ atoms/ion) of H from hydrogenated MCT wafers is observed due to the bombardment with 80 MeV Ni⁹⁺ ions. The initial H areal concentration and hydrogen depletion rate is monitored by elastic recoil detection analysis. The ion-damaged zones from where depletion of H takes place have been calculated from fluence-dependent hydrogen areal content analysis. The results are explained on the basis of the thermal spike model of ion-solid interaction.     

Effect of thermo-mechanical processing on microstructure and creep properties of the foils of alloy 617

The effect of rolling and annealing on the microstructure and high temperature creep properties of alloy 617 were investigated. Two types of foil specimens with different thickness reductions were prepared by thermo-mechanical processing. Recrystallization and grain growth were readily observed at specimens annealed at 950 and 1100 °C. The uniform coarse grains increase resistance against creep deformation. The grain size effect in creep deformation was dominant up to 900 °C, while dynamic recrystallization effect became dominant at 1000 °C. Dynamic recrystallization was observed in all the creep deformed foils, even though some specimens had already been (statically) recrystallized during annealing. Steady state creep rates decreased with increasing annealing temperature in the less rolled foils. The apparent activation energy Q_app for the creep deformation increased from 271 to 361 kJ/mol as the annealing temperature increased from 950 to 1100 °C.