Radiation cross-linking in ultra-high molecular weight polyethylene for orthopaedic applications

The motivation for radiation cross-linking of ultra-high molecular weight polyethylene (UHMWPE) is to increase its wear resistance to be used as bearing surfaces for total joint arthroplasty. However, radiation also leaves behind long-lived residual free radicals in this polymer, the reactions of which can detrimentally affect mechanical properties. In this review, we focus on the radiation cross-linking and oxidative stability of first and second generation highly cross-linked UHMWPEs developed in our laboratory.     

Vitamin C hinders radiation cross-linking in aqueous poly(vinyl alcohol) solutions

Poly(vinyl alcohol) (PVA) is a promising semi-crystalline material for biomedical applications. It is soluble in water and can be formed into hydrogels by freezing and thawing or crystallizing from an aqueous theta solution such as that of polyethylene glycol (PEG). Radiation cross-linking caused by sterilization or high dose irradiation of concentrated PVA solutions could compromise some properties of these hydrogels. Therefore, we hypothesized that radiation cross-linking of PVA solutions and PVA-PEG theta gels could be prevented by using the antioxidant vitamin C as an anticross-linking agent. Our hypothesis tested positive. Vitamin C concentrations of 0.75 and 4.5 mol/mol of PVA repeating unit could prevent cross-linking in 17.5 wt/v% PVA solutions made with PVA molecular weight of 115,000 g/mol irradiated to 25 and 100 kGy, respectively. Vitamin C also prevented cross-linking in 25 kGy irradiated PVA-PEG theta gels containing up to 5 wt% PEG and decreased the viscosity of those up to 39 wt%.     

Strain-driven (0 0 2) preferred orientation of ZnO nanoparticles in ion-implanted silica

We present an experimental and theoretical study on the structural properties of ZnO nanoparticles embedded in silica. The ZnO-SiO₂ nanocomposite was prepared by ion implanting a Zn⁺ beam in a silica slide and by annealing in oxidizing atmosphere at 800 °C. From an experimental point of view, the structural properties of the ZnO-SiO₂ nanocomposite were studied by using glancing incidence X-ray diffraction. According to the results, zinc crystalline nanoclusters with an average diameter of 13 nm are in the as-implanted sample. The annealing in oxidizing atmosphere promotes the total oxidation of the Zn nanoclusters and increases their size until to an average of 22 nm. Moreover, the formed ZnO nanocrystals have a preferential (0 0 2) crystallographic orientation. From a theoretical point of view, the preferential orientation of the ZnO nanoparticles can be explained satisfactory by the minimization of the strain energy of the nanoparticles placed in proximity of the surface of the matrix.     

Radiation-induced degradation of galactomannan polysaccharides

In this study, guar gum, tara gum and locust bean gum were irradiated in a gamma cell in the solid state. The change in their molecular weights were determined by size exclusion chromatography analysis and the change in their viscosity values with change of temperature and irradiation dose were determined. Chain scission yield, G(s), and degradation rate values were calculated. The calculated G(s) values is 1.09 ± 0.16, 1.07 ± 0.06, 0.85 ± 0.10 for GG, TG and LBG, respectively. The effect of mannose-galactose ratio and initial molecular weight of these gums on the degradation behavior were discussed.     

Influence of asymmetric etching on ion track shapes in polycarbonate

By combining low-energy ion irradiation with asymmetric etching, conical nanopores of controlled geometry can be etched in polycarbonate (PC). Cone bases vary from 0.5 to 1 μm. Top diameters down to 17 nm are reached. When etching from one side, the pH on the other side (bathed in neutral or acidic buffer) was monitored. Etching temperature ranged from 65 °C to 80 °C. Pore shape characterization was achieved by electro replication combined with SEM observation. The tip shape depended on whether an acidic buffer was used or not on the stopped side.     

Ion beam induced defects in solids studied by optical techniques

Optical methods can provide important insights into the mechanisms and consequences of ion beam interactions with solids. This is illustrated by four distinctly different systems.X- and Y-cut LiNbO₃ crystals implanted with 8 MeV Au³⁺ ions with a fluence of 1 × 10¹⁷ ions/cm² result in gold nanoparticle formation during high temperature annealing. Optical extinction curves simulated by the Mie theory provide the average nanoparticle sizes. TEM studies are in reasonable agreement and confirm a near-spherical nanoparticle shape but with surface facets. Large temperature differences in the nanoparticle creation in the X- and Y-cut crystals are explained by recrystallisation of the initially amorphised regions so as to recreate the prior crystal structure and to result in anisotropic diffusion of the implanted gold.Defect formation in alkali halides using ion beam irradiation has provided new information. Radiation-hard CsI crystals bombarded with 1 MeV protons at 300 K successfully produce F-type centres and V-centres having the structure as identified by optical absorption and Raman studies. The results are discussed in relation to the formation of interstitial iodine aggregates of various types in alkali iodides. Depth profiling of and aggregates created in RbI bombarded with 13.6 MeV/A argon ions at 300 K is discussed.The recrystallisation of an amorphous silicon layer created in crystalline silicon bombarded with 100 keV carbon ions with a fluence of 5 × 10¹⁷ ions/cm² during subsequent high temperature annealing is studied by Raman and Brillouin light scattering.Irradiation of tin-doped indium oxide (ITO) films with 1 MeV protons with fluences from 1 × 10¹⁵ to 250 × 10¹⁵ ions/cm⁻² induces visible darkening over a broad spectral region that shows three stages of development. This is attributed to the formation of defect clusters by a model of defect growth and also high fluence optical absorption studies. X-ray diffraction studies show evidence of a strained lattice after the proton bombardment and recovery after long period storage. The effects are attributed to the annealing of the defects produced.     

Mechanical properties of Eurofer 97 in Pb-16Li and irradiation effect

To be used in a fusion reactor, structural materials, and in particular steels, has to be selected and optimised in their composition to achieve a reduction in the long-term radioactive waste. A reduction in the long-term radioactive inventory could be reached substituting elements like molybdenum, niobium and nickel with other ones like tantalum and tungsten which have the same functions as alloying elements and, if irradiated, do not produce long lived radioisotopes. The martensitic steel belonging to the family of 8-9% Cr Eurofer 97 is considered the reference structural steel for fusion application. However, only few information are available about its mechanical properties in the liquid eutectic alloy Pb-16%Li. Particularly, the problem of liquid metal embrittlement (LME) has not been studied in detail and the effect of neutron irradiation on LME has not been investigated at all so far. This work presents the results obtained irradiating tensile specimens of Eurofer 97 up to 5.9 dpa in lead lithium. Tensile tests of samples have been performed out of pile in the same alloy at the same temperature at which irradiation was carried out.     

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.     

Irradiation-induced precipitation modelling of ferritic steels

In high strength low alloy (HSLA) steels typically used in reactor pressure vessels (RPV), irradiation-induced microstructure changes affect the performance of the components. One such change is precipitation hardening due to the formation of solute clusters and/or precipitates which form as a result of irradiation-enhanced solute diffusion and thermodynamic stability changes. The other is irradiation-enhanced tempering which is a result of carbide coarsening due to irradiation-enhanced carbon diffusion. Both effects have been studied using a recently developed Monte Carlo based precipitation kinetics simulation technique and modelling results are compared with experimental measurements. Good agreements have been achieved.     

Investigation of the sensitivity to EAC of steel T91 in contact with liquid LBE

The ferritic-martensitic steel T91 is one of the most promising material for application in the generation IV type reactors. However, there are critical issues, such as the susceptibility to damage of the steel in contact with the heavy liquid metals and their effect on the mechanical properties of structural materials. In this context, it was initiated a study of the boundary conditions, necessary to ascertain the sensitivity of the T91 to environmentally assisted cracking when loaded in contact with the liquid lead-bismuth eutectic. A series of tensile tests were carried out in a cell where the specimens were immersed in static LBE. Results showed that at high temperature the steel in contact with the liquid metal had a slight decrease of yield and UTS value and a marked increase in the elongation to rupture. However, at low temperature the elongation to rupture and the reduction of area decreased, indicating the sensitivity to EAC.     

Application of ionizing radiations to produce new polysaccharides and proteins with enhanced functionality

Treatment of polysaccharides with ionizing radiation either in the solid state or in aqueous solution leads to degradation. Using a mediating alkyne gas during the radiation treatment prevents the degradation of natural and synthetic polysaccharides and enables the introduction of different molecular and functional characteristics, as previously achieved with synthetic polymers. The molecular weight can be increased and hydrogel forms of the polysaccharides or proteins can be produced, probably by a cross-linking mechanism involving addition of C-C bond between two chains. The product has higher viscosity and is more elastic than the original material and, therefore, gives enhanced functionality. Gum Arabic (Acacia senegal) irradiated for 6.2 kGy is used here to demonstrate the enhanced emulsification performance and stability compared with the original material.     

Experimental study of the response of radiochromic films to proton radiation of low energy

We have investigated the response of radiochromic films (MD-55 and HD-810) exposed to protons of 0.6 MeV. Each film is bombarded with a proton beam in an angular geometry, in such a way that the absorbed dose is related to angle. Depending on the energy and the angular fluence, the irradiated volume is total or partial. We compare the dose of these irradiated films with fully irradiated films exposed to γ radiation from a ⁶⁰Co calibrated source.     

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.     

A sensitive EPR dosimetry system based on sulfamic acid

There is a need for a sensitive dosimeter using electron paramagnetic resonance spectroscopy (EPR) for use in medical applications, since with this method non-destructive read-out and dose archival could be achieved. Sulfamic acid as a possible detector substance was investigated before and after irradiation, its EPR spectra were recorded and analyzed, some dosimetric characteristics were studied: microwave power saturation behavior, the effect of modulation amplitude on peak-to-peak signal intensity and the line width. Energy-dependence parameters were compared to soft tissue and alanine, and the response to ionizing radiation was studied, also the decay behavior along 133 days after irradiation is presented. It is found that sulfamic acid possesses high-sensitivity and reasonable signal stability which may make it useful as a sensitive dosimeter for medical applications.     

Radiation effects in cubic zirconia: A model system for ceramic oxides

Ceramics are key engineering materials for electronic, space and nuclear industry. Some of them are promising matrices for the immobilization and/or transmutation of radioactive waste. Cubic zirconia is a model system for the study of radiation effects in ceramic oxides. Ion beams are very efficient tools for the simulation of the radiations produced in nuclear reactors or in storage form. In this article, we summarize the work made by combining advanced techniques (RBS/C, XRD, TEM, AFM) to study the structural modifications produced in ion-irradiated cubic zirconia single crystals. Ions with energies in the MeV-GeV range allow exploring the nuclear collision and electronic excitation regimes. At low energy, where ballistic effects dominate, the damage exhibits a peak around the ion projected range; it accumulates with a double-step process by the formation of a dislocation network. At high energy, where electronic excitations are favored, the damage profiles are rather flat up to several micrometers; the damage accumulation is monotonous (one step) and occurs through the creation and overlap of ion tracks. These results may be generalized to many nuclear ceramics.     

Influence of a surfactant on single ion track etching: Preparing and manipulating cylindrical micro wires

The influence of the alkali resistant surfactant Dowfax 2A1 on single ion track etching in 30 μm polycarbonate foils is studied at low etch rate (5 M NaOH at 41.5 ± 2 °C) using electro conductivity measurements. At surfactant concentrations above 10⁻⁴ vol.% break-through times are predictable (Δt/t < 0.25). At high surfactant concentrations (?0.1 vol.%) the formation of cylindrical channels is favoured. The shape of these channels (length ? 26 μm, diameter ? 1.8 μm) is verified by electro-replication and SEM observation of the resulting wires. Agreement of radii is better than 0.1 μm. Depending on the current limit set during electro replication compact or hollow cylinders can be obtained. A technique for localizing and manipulating individual micro wires by their head buds is described.     

Caesium isothermal migration behaviour in sintered titanium nitride: New data and comparison with previous results on iodine and xenon

Titanium nitride has been proposed as a fission product barrier in fuel structures for gas cooled fast reactor (GFR) systems. The thermal migration of Cs was studied by implanting 800 keV ¹³³Cs⁺⁺ ions into sintered samples of TiN at an ion fluence of 5 × 10¹⁵ cm⁻². Thermal treatments at temperatures ranging from 1500 to 1650 °C were performed under a secondary vacuum. Concentration profiles were determined by 2.5 MeV ⁴He⁺ elastic backscattering. The results reveal that the global mobility of caesium in the host matrix is low compared to xenon and iodine implanted in the same conditions. Nevertheless, the evolution of caesium depth profile during thermal treatment presents similarities with that of xenon. Both species are homogeneously transported towards the surface and the transport rate increases with the temperature. In comparison, iodine exhibits singular migration behaviour. Several assumptions are proposed to explain the better retention of caesium in comparison with both other species. The potential role played by the oxidation is underlined since even a slight modification of the surface stoichiometry may modify species mobility. More generally, the apparition of square-like shapes on the surface of the samples after implantations and thermal treatments is discussed.     

Interdiffusion of polydisperse Mw distributions subsequent to proton irradiation of PS melts

Under exposure to ionizing radiation the molecular weights of polymeric matter changes via formation of crosslinks and scissions of chains. As a result the molecular weight (M_w) distribution of a polymer depends on the applied ion fluence and differs from the initial one, which in our case is of the Schulz-Zimm type. Statistical theories can be used to estimate the M_w distribution.We study M_w distributions in proton irradiated polystyrene (PS) thin films by diffusion measurements. As chains of different degrees of polymerization diffuse unequally fast diffusion depth profiles contain information about the involved M_w distribution. Both irradiation and analysis with nuclear reaction analysis (NRA) were made at the Freiburg van de Graaff accelerator.As comparison gel permeation chromatography (GPC) measurements were conducted. However, the use of GPC is limited by the minimal amount of material needed and also does not work for very short chains in our case.Here we concentrate on the M_w distributions, the measurements and the fitting procedure will be presented elsewhere.