Comparative study of different initiation methods in the functionalization of low-density polyethylene with diethyl maleate: Gamma radiation and ultrasound

This work unfolds a comparative study of the grafting of a low-density polyethylene with diethyl maleate (DEM) using gamma irradiation and ultrasound as means of initiating the grafting reactions. The grafting degree was determined by FTIR using a reported calibration curve. The efficiency of both functionalization methodologies was calculated and the polymers were characterized by differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The results showed that the grafting degree increases with the radiation dose when the monomer is inserted by gamma radiation. When the ultrasound methodology was used, an additional initiator such as dicumyl peroxide had to be used in order for the grafting to take place. In this last case, changing the time of exposure to the ultrasound source did not induce significant changes in the obtained grafted degree. The use of ultrasonic radiation plus dicumyl peroxide as grafting initiators promoted more insertion than that when gamma radiation was employed.     

Improvement on thermoelectric properties of multilayered Si1−xGex/Si by ion beam bombardment

We made n-type nano-scale thin film thermoelectric (TE) devices that consist of multiple periodic layers of Si_1−xGe_x/Si. The period is about 10 nm. The structure was modified by 5 MeV Si ion bombardment that formed a nano-scale cluster structure. In addition to the effect of confinement of the phonon transmission, formation of nanoclusters by the ionization energy of incident MeV Si ions further increases the scattering of phonons, increasing the chance of inelastic interaction of phonons, resulting in more annihilation of phonons. This limits phonon mean free path. Phonons are absorbed and dissipated along the layers rather than in the direction perpendicular to the layer interfaces, therefore cross plane thermal conductivity is reduced. The increase of the density of electronic states due to the formation of nanocluster minibands increases the cross plane Seebeck coefficient and increases the cross plane electric conductivity of the film. Eventually, the thermoelectric figure of merit of the TE film increases.     

Hybrid PDMS-Silica-Zirconia materials prepared by γ-irradiation

Hybrids are a class of materials that enable the integration of organic and inorganic characteristics at the molecular level in a single material. In this way materials with unusual optical, mechanical or even bioactive properties are obtained, which are especially suitable for applications as sensors, non-linear optical (NLO) materials, lasers, selective membranes, catalysts and protective coatings. Sol-gel processing is often used for the preparation of hybrids, usually through the alkoxides method that leads to high purity products at relatively low temperatures. The authors have developed a new method for the preparation of these materials based on gamma irradiation of the precursors mixture. The precursors used are polydimethylsiloxane (PDMS), tetraethylortosilicate (TEOS) and zirconium propoxide (PrZr). The irradiations were performed using the ⁶⁰Co source at the Portuguese Gamma Irradiation Facility (UTR) located in the ITN campus at Sacavém. The materials at room temperature are macroscopically transparent, relatively flexible and amorphous. The details of the preparation of these hybrid materials by gamma irradiation are presented.     

New conductive copolymer membranes via track-etched PC templates for biological media ultra-filtration

New microstructurated copolymer membranes have been synthesized using a track-etched polycarbonate (PC) matrix. These membranes proved to be an important device in the field of ultra-filtration and synthetic membranes. These novel structures were obtained by irradiating at various angles (+30°, −30°). Such architecture is expected to improve not only the exchange properties but also, the behaviour under high flow pressure during their use as nanofiltration membranes. Membrane functionalization was performed with an amino acid as a simple biological model. Transmission and ATR-FTIR spectroscopies show that the doping state of copolymer dramatically influences the amino acid coupling rate. UV-vis spectroscopy indicates that the copolymer may be self-doped.     

ECR plasma assisted deposition of zinc nanowires

Deposits of one dimensional nanowires of zinc with diameters of 90-120 nm have been obtained by means of dc sputtering within an electron cyclotron resonance plasma reactor. The sputtering has been made effective by using a negatively biased cylindrical target. The structure of the nanocrystalline wires deposited on glass substrates were investigated with scanning electron microscopy, transmission electron microscopy and scanning tunneling microscopy. STM revealed that the structure of the one dimensional nanowires are ensemble of nanoclusters and nanowires with diameter of 4-5 nm. The crystalline nature of the metallic nanowires was studied with X-ray and electron diffraction analysis. The native oxide present on the metallic wires was revealed by photoluminescent spectroscopy. Theoretical modeling has been used to explain the possible mechanisms operative inside the plasma which lead into deposition of zinc on the substrate starting from the precursor species.     

Determination of bulk etch rate for CR-39 nuclear track detectors using an X-ray fluorescence method

The thickness of a CR-39 detector is determined using an energy dispersive X-ray fluorescence (EDXRF) method of analysis. The method is based on exciting a suitable target and measuring the intensity of its fluorescence X-ray lines passing through the CR-39 sample in a fixed geometry. By properly selecting the target material, the method succeeds in assessing the thickness change of CR-39 detectors etched for different time intervals. The bulk etch rate (V_b) may thus be obtained, which is an important parameter for any solid state nuclear track detector. Application of the EDXRF method yielded a value of V_b = (2.01 ± 0.04) μm h⁻¹ for etching in a 6 N NaOH solution at 75 °C. This value agrees with the bulk etch rate of (1.90 ± 0.03) μm h⁻¹, obtained by the conventional mass-change method.     

Diode-like ion-track asymmetric nanopores: Some alternative methods of fabrication

We present two fabrication methods which allow production of ion-track nanopore membranes with pronounced geometrical asymmetry and diode-like ionic conductivity. The asymmetry of the pores is provided by self-assembly of surfactant molecules at ion-track entrances on one side of the ion-irradiated polymer foil. On the other side of the membrane, the effect of surfactant is excluded using a pre-treatment with ultraviolet radiation or a surfactant-free etching solution. Highly tapered pore profiles are obtained and characterized using SEM and FESEM. In electrolyte solutions, the asymmetric pores thus fabricated exhibit a high rectification of electric current. The nanopores with a large angle aperture can be of interest for resistive-pulse technique applications and for the atomic beam projection nanolithography.     

Novel way to control PDMS cross-linking by gamma-irradiation

Using a ⁶⁰Co gamma source polydimethylsiloxane-based materials have been prepared by gamma-irradiation of a mixture of polydimethylsiloxane, PDMS, silanol-terminated and the tetraethylortosilicate, TEOS, with no other chemicals. Samples were prepared with varying TEOS concentrations. The obtained materials are monolithic, flexible and transparent. X-ray measurements have shown them to be amorphous. The thermal behaviour has also been investigated by using differential scanning calorimetry and thermal gravimetric analysis. The results suggest that TEOS have a tailoring effect on the conformation of the polymer chains, affecting the network formation, as shown by the swelling behaviour of the material.     

Photon interaction and energy absorption in glass: A transparent gamma ray shield

The effective atomic number, Z_eff, the effective electron density, N_e,eff, and the energy dependence, ED, have been calculated at photon energies from 1 keV to 1 GeV for CaO-SrO-B₂O₃, PbO-B₂O₃, Bi₂O₃-B₂O₃, and PbO-Bi₂O₃-B₂O₃ glasses with potential applications as gamma ray shielding materials. For medium-Z glasses, Z_eff is about constant and equal to the mean atomic number in a wide energy range, typically 0.3 < E < 4 MeV, where Compton scattering is the main photon interaction process. In contrast, for high-Z glasses there is no energy region where Compton scattering is truly dominating. Heavy-metal oxide glasses containing PbO and/or Bi₂O₃ are promising gamma ray shielding materials due to their high effective atomic number and strong absorption of gamma rays. They compare well with concrete and other standard shielding materials and have the additional advantage of being transparent to visible light. The single-valued effective atomic number calculated by XMuDat is approximately valid at low energies where photoelectric absorption is dominating.     

Optimization of nanopores obtained by chemical etching on swift-ion irradiated lithium niobate

The morphology of the nanopores obtained by chemical etching on ion-beam irradiated LiNbO₃ has been investigated for a variety of ions (F, Br, Kr, Cu, Pb), energies (up to 2300 MeV), and stopping powers (up to 35 keV/nm) in the electronic energy loss regime. The role of etching time and etching agent on the pore morphology, diameter, depth, and shape has also been studied. The transversal and depth profiles of the pore have been found to be quite sensitive to both irradiation and etching parameters. Moreover, two etching regimes with different morphologies and etching rates have been identified.     

Nanoporous β-PVDF membranes with selectively functionalized pores

Poly(vinylidene fluoride) (β-PVDF) nanoporous membranes are obtained by heavy ion irradiation and track etching leading to cylindrical pores. Pores diameter measured by scanning electron microscopy and small angle neutron scattering lies in the 20-50 nm range. Electron paramagnetic resonance study gives evidence that radicals still remains in PVDF membrane after track-etching. These radicals allows acrylic acid polymerization to be initiated onto membrane. Radiografted and functionalized membranes are characterized using infrared spectroscopy and weighing. Finally, radiografted poly(acrylic acid) (PAA) has been selectively labeled by fluorophores and imaged by confocal laser scanning microscopy. Images show the localisation of PAA specifically inside nanopores.     

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).     

Radiation grafting of methyl methacrylate onto polyethylene separators for lithium secondary batteries

Micro-porous polyethylene separator was modified by radiation grafting of methyl methacrylate in order to improve its affinity with a liquid electrolyte. The degree of grafting (DOG) increased with the monomer concentration and grafting time. The morphological change of the modified separator was investigated by scanning electron microscopy. The degree of crystallinity upon grafting was reduced due to the formation of an amorphous PMMA layer. The electrolyte uptake and the ionic conductivity of the separator increased with an increase in the DOG. The ionic conductivity reached 2.0 mS/cm for the grafted polyethylene separator with 127 wt% DOG.     

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.     

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.     

Imaging dynamics of charge-auto-organisation in glass capillaries

Multiply charged ion beam transmission through insulating capillaries is today a very active field of research. Thanks to the work of several groups during the last five years, several features of this unexpected process have been evidenced. The open challenge is to understand and control the self-organized charging-up of the capillary walls, which leads finally to the ion transmission. Up to now, the specific charge distribution on the inner surface, as well as the dynamics of the build-up, are still to be understood. While capillaries usually studied are microscopic pore networks etched in different materials, our concern is in macroscopic single capillaries made of glass. With a length of several centimeters and a diameter of a few micrometers at the exit, these capillaries have nevertheless the same aspect ratio as the etched pores (length/diameter ≈ 100). One of the leading goals of this research on single capillaries is to produce multi-charged ion beams with diameters smaller than a micrometer (nano-beams). These glass capillaries offer the opportunity to be used as an ion funnel due to their amazing properties of guiding and focusing highly charged ion beams without altering neither their initial charge state nor the beam emittance (<10⁻³ π mm mrad). However, the understanding of the underlying process is not complete and relies on models assuming charge patches distributed along the capillary and which still need to be tested. We present the first observation imaging the dynamics of the charging-up process in single glass capillaries. During the build-up of the self-organized charge deposition on the capillary walls, the 230 keV Xe²³⁺ transmitted beam is deflected back and forth several times as the outgoing current increases. This is in agreement with the picture of charge patches created sequentially along the capillary and thus deflecting the beam until a stationary state is reached.     

The peculiarities of formation of the metal nanoparticles in irradiated polymer metal complexes

The radiation-induced reduction of metal ions in the films of triple metal polymer complexes of polyacrylic acid-polyethyleneimine-copper(II) or nickel(II) (PAA-PEI-Cu²⁺ or PAA-PEI-Ni²⁺) was studied by EPR and transmission electron microscopy (TEM). It was shown that irradiation of the swollen polymer films in the water-alcohol environment resulted in effective reduction of the metal ions. The exchange between the swollen film and outer environment was found to be an important factor for ion reduction and stabilization of metal particles. EPR data have revealed pronounced effect of the ligand environment on the reduction efficiency. The electron microscopy studies have demonstrated that the dimensions of main fraction of metal particles obtained by the radiation-chemical reduction are in the range of 2-2.5 nm both for Cu and for Ni complexes.     

Design of an ion extractor system for a prototype ion source experiment for SST-1 neutral beam injector

An ion extractor system has been designed for the steady state superconducting tokamak (SST-1) neutral beam injector (NBI) for an experiment using a prototype ion source with fully integrated regulated high voltage power supply (RHVPS) and data acquisition and control system (DACS) developed at Institute for Plasma Research (IPR) to obtain experience of NB operation. The extractor system is capable of extracting positive hydrogen ion beam of ∼10 A current at ∼20 kV. This paper presents the beam optics study for detailed design of an ion extraction system which could meet this requirement. It consists of 3 grid accel-decel system, each of the grid has 217 straight cylindrical holes of 8 mm diameter. Grids are placed on a specially designed G-10 block; a fiber reinforc plastic (FRP) isolator of outer diameter of 820 mm and 50 mm thickness. Provisions are made for supplying high voltage to the grid system through the embedded feed-throughs. Extractor system has been fabricated, mounted on the SST-1 neutral beam injector and has extracted positive hydrogen ion beam of 4 A at 20 kV till now.     

Ion beam characterization of rf-sputter deposited AlN films on Si(1 1 1)

Aluminum nitride (AlN) thin films have been deposited on Si(1 1 1) substrates by using reactive-rf-magnetron-sputtering at 250 °C. The crystalline quality and orientation of the films have been studied by X-ray diffraction (XRD). We have observed that the films grow with c- or a-axis orientation. The composition, film thickness, impurities and stress are considered to be factors affecting the orientation and have been analyzed by Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA) and XRD. Their effects on the film growth will be discussed. Surface morphology of the films will be also presented.