A method for rapid determination of the relative concentration of hydrogen isotopes in aqueous solutions was developed based on the rapid measurement of the different molecular bending vibrations using Fourier transform infrared (FTIR) spectroscopy. Isotopic H2O and D2O mixtures (with D2O concentration varying from 0%-100%) were examined in the liquid phase under different environments to estimate the stability, repeatability, and accuracy of FTIR spectroscopy as a rapid assay technique for heavy and light water mixtures. The generated results suggested a high agreeability with the simulated equilibrium constant of the water mixture (average deviation close to 1%) after considering the existence of HDO in the solution. The high sensitivity of the molecular bending motion in detecting the isotopic variations of hydrogen (approximately 0.5%) also proved the reliability of applying FTIR spectroscopy in isotopic determinations. Therefore, we suggested a relatively accurate and rapid identification method for determining the relative proportion of hydrogen isotopes in an aqueous solution by measuring and ratiating the relative peak intensity of the FTIR recorded vibrational peaks.

Creep in metal alloys is an important failure mode for high temperature and stress applications, but despite extensive study it is still not fully understood, particularly the early stage of creep cavity formation. This paper describes a novel constant load cantilever beam test to investigate creep damage and cavitation at grain boundaries in copper bicrystals. Bicrystals of copper have been prepared with the grain boundary oriented normal to the beam long axis, allowing the development of damage at a single boundary to be studied. Tests were conducted at a temperature of 285°C in a vacuum of 10−10 MPa. Creep cavitation is observed in copper bicrystals of {001} and {111} orientation with a 22° rotation at the boundary. We compare these data with observations for a polycrystalline copper specimen.

Creep in metals and alloys has been observed and studied extensively over the past century. Most studies are based on constant load or less frequently on constant stress conditions. Under certain stress regimes during the period of service, such as creep-fatigue (cyclic), and under displacement-controlled loading the stress can relax. This paper uses novel millimetre length-scale beam bend geometry test specimens with constant displacement to simulate stress relaxation and explore cavity nucleation and early-stage growth/closure in a model poly-crystalline material, namely oxygen-free high-conductivity copper. The role of changing grain size over the range 43 & mu;m-2350 & mu;m has been explored. Power-law creep theoretical modelling and finite element analyses have been adopted to predict creep relaxation and explain cavity nucleation and early-stage growth/closure for the test conditions. The results are compared with the experimental observations. The overall experimental and modelling outcomes are considered with respect to the underlying creep damage mechanism.

Synthetic polygranular graphites have a wide range of current and potential applications. Indeed, some are being considered as candidate moderator materials for the next generation of nuclear power plants, which are designed to operate at temperatures as high as 1000 °C. Detailed experimental work has been performed to investigate the electrical resistivity and mechanical behaviour of a synthetic graphite over a range of temperatures. An electrothermomechanical testing rig has been employed to conduct tensile tests to evaluate elastic modulus and fracture strength over the temperature range from room temperature to 700 °C for a near-isotropic synthetic polygranular graphite. A series of mm length scale ‘dogbone’ geometry specimens, containing varying levels of porosity between 8% and 18%, were used for testing. Acquired data revealed an average of 30% gain in material stiffness, occurring at temperatures above 400 °C. Tensile strength decreased linearly with increasing porosity at higher temperatures (700 °C). The accumulated percentage reduction of resistivity during the transition from room temperature to 700 °C reduced linearly with increasing amounts of porosity. The resistivity and mechanical property measurements are discussed, with particular attention given to the porosity of the synthetic graphite.

A primary target towards the clean-up operation of the Fukushima disaster is the retrieval of Molten Core-Concrete Interaction (MCCI) products, presently residing on the basement of the damaged nuclear reactor Units 1–3. MCCI is a fusion of materials, composed of both nuclear fuel cladding and neighbouring structural components. Determining the currently unknown, physical and mechanical properties of MCCI is essential for successful and timely retrieval. In this paper, we aim to experimentally quantify the mechanical properties of a material fabricated to resemble MCCI. A small-scale representative specimen was mechanically tested using Hertzian indentation stepwise loading. Synchrotron X-ray computed tomography was conducted at several loading stages to reveal the sample microstructure and mechanical degradation. The acquired tomograms were analysed by digital volume correlation to measure full-field displacements and strains developed within the sample volume. Young’s modulus and Poisson ratio were determined via this combined methodology.

Synthetic polygranular graphites of various grades and manufacturing routes are used in nuclear reactors for power generation, and may be used in potential fourth generation and other advanced reactor designs that will operate at higher temperature. Attention is given in this paper to isostatically-moulded synthetic polygranular graphites with porosities in the range 8% to 18%. The lattice parameters a and c for the hexagonal graphite have been measured over the temperature range from room temperature to 800°C by x-ray diffraction. The variation with temperature of the crystal lattice parameters, coherence length (crystallite size) and microstrain are discussed with reference to the microstructure and the relative strength of the bonds in-plane and normal to the graphene layers.

Decommissioning of the damaged Chernobyl nuclear reactor Unit 4 is a top priority for the global community. Before such operations begin, it is crucial to understand the behaviour of the hazardous materials formed during the accident. Since those materials formed under extreme and mostly unquantified conditions, modelling alone is insufficient to accurately predict their physical, chemical and, predominantly, mechanical behaviour. Meanwhile, knowledge of the mechanical characteristics of those materials, such as their strength, is a priority before robotic systems are employed for retrieval and the force expected from them to be exerted is one of the key design questions. In this paper we target to measurement of the standard mechanical properties of the materials formed during the accident by testing small-scale, low radioactivity simulants. A combined methodology using Hertzian indentation, synchrotron X-ray tomography and digital volume correlation (DVC), was adopted to estimate the mechanical properties. Displacement fields around the Hertzian indentation, performed in-situ in a synchrotron, were measured by analysing tomograms with DVC. The load applied during the indentation, combined with full-field displacement measured by DVC was used to estimate the mechanical properties, such as Young's modulus and Poisson's ratio of these hazardous materials.

MXene-based hybrid composites are gaining substantial attention due to their impressive chemical and electronic characteristics. Herein, an in-situ engineered heterojunction is constructed using partially-oxidised Ti3C2Tx sheets and photo-active NiWO4 nanoparticles (NPs). The NiWO4 NPs were used to induce partial surface oxidation of Ti3C2Tx, resulting in the formation of a Ti3C2Tx-TiO2/NiWO4 hybrid composite (MX-NiWO4). The electrocatalytic and photo-electrochemical (PEC) characteristics of MX-NiWO4 were studied in reference to the reduced graphene oxide-NiWO4 (rGO-NiWO4) and H2O2-treated Ti3C2Tx (MX-H2O2) hybrids. The MX-NiWO4, based on its in-situ driven configuration, constructed an ideal interfacial arrangement for the electrocatalytic mechanism-based PEC immuno-sensing of prostate-specific antigens (PSA). The developed PEC biosensor was capable of detecting PSA, over a wide detection range of 1.2 fg.mL(-1) to 0.18 mg.mL(-1), with a detection limit of 0.15 fg.mL(-1). The synergic integration of Ti3C2Tx with photo-active NiWO4 offers a superior signal response and practical applicability when used for the quantification of PSA from human saliva samples, anticipating the hybrid's promising future in clinical detection.

Background: Aseptic loosening of total joint replacements (TJRs) continues to be the main cause of implant failures. The socioeconomic impact of surgical revisions is hugely significant; in the United Kingdom alone, it is estimated that 137 pound m is spent annually on revision arthroplasties. Enhancing the longevity of titanium implants will help reduce the incidence and overall cost of failed devices. Methods: In realising the development of a superior titanium technology, we exploited the natural affinity of titanium for phosphonic acids and developed a facile means of coating the metal with (3S)1-fluoro-3-hydroxy-4-(oleoyloxy)butyl-1-phosphonate (FHBP), a phosphatase-resistant analogue of lysophosphatidic acid (LPA). Importantly LPA and selected LPA analogues like FHBP synergistically cooperate with calcitriol to promote human osteoblast formation and maturation. Results: Herein, we provide evidence that simply immersing titanium in aqueous solutions of FHBP afforded a surface that was superior to unmodified metal at enhancing osteoblast maturation. Importantly, FHBP-functionalised titanium remained stable to 2 years of ambient storage, resisted similar to 35 kGy of gamma irradiation and survived implantation into a bone substitute (Sawbone (TM)) and irrigation. Conclusion: The facile step we have taken to modify titanium and the robustness of the final surface finish are appealing properties that are likely to attract the attention of implant manufacturers in the future. The translational potential of this article: We have generated a functionalised titanium (Ti) surface by simply immersing Ti in aqueous solutions of a bioactive lipid. As a facile procedure it will have greater appeal to implant manufacturers compared to onerous and costly developmental processes.

During the early years of nuclear industry within the UK, the typical route followed to handle Magnox (Mg-Al alloy) casing after separation from the nuclear fuel has been immersion in water temporarily in specifically-designed water ponds. Over the decades of storage, Magnox has been corroding in water, resulting in the formation of sludge within the ponds; known as Corroded Magnox Sludge. Uranium, which has been also contained within the ponds as a result of faults occurring during fuel-casing separation, is susceptible to corrosion in waterrich environments. Under certain circumstances, uranium corrosion products can be highly pyrophoric during oxidation in air. This raises serious concerns regarding the safety margins of nuclear pond decommissioning. The present study attempts to shed light on the behaviour of uranium in a Magnox sludge-surrogate environment, using X-ray computed tomography at distinct time intervals over an 18-month period. Focus was given onto the uranium-sludge interface to determine metallic corrosion onset and evolution.

Both the three-dimensional internal structure and elemental distribution of near-field radioactive fallout particulate material released during the March 2011 accident at the Fukushima Daiichi Nuclear Power Plant is analysed using combined high-resolution laboratory and synchrotron radiation x-ray techniques. Results from this study allow for the proposition of the likely formation mechanism of the particles, as well as the potential risks associated with their existence in the environment, and the likely implications for future planned reactor decommissioning. A suite of particles is analyzed from a locality 2 km from the north-western perimeter of the site – north of the primary contaminant plume in an area formerly attributed to being contaminated by fallout from reactor Unit 1. The particles are shown to exhibit significant structural similarities; being amorphous with a textured exterior, and containing inclusions of contrasting compositions, as well as an extensive internal void volume – bimodal in its size distribution. A heterogeneous distribution of the various elemental constituents is observed inside a representative particle, which also exhibited a Fukushima-derived radiocesium (134Cs, 135Cs and 137Cs) signature with negligible natural Cs. We consider the structure and composition of the particle to suggest it formed from materials associated with the reactor Unit 1 building explosion, with debris fragments embedded into the particles surface. Such a high void ratio, comparable to geological pumice, suggests such material formed during a rapid depressurisation and is potentially susceptible to fragmentation through attrition.

The appraisal is strongly focussed on challenges associated with the nuclear sector, however these are representative of what is generally encountered by a range of engineering applications. Ensuring structural integrity of key nuclear plant components is essential for both safe and economic operation. Structural integrity assessments require knowledge of the mechanical and physical properties of materials, together with an understanding of mechanisms that can limit the overall operating life. With improved mechanistic understanding comes the ability to develop predictive models of the service life of components. Such models often require parameters which can be provided only by characterisation of processes occurring in situ over a range of scales, with the sub-micrometre-scale being particularly important, but also challenging. This appraisal reviews the techniques currently available to characterise microstructural features at the nanometre to micrometre length-scale that can be used to elucidate mechanisms that lead to the early stages of environmentally-assisted crack formation and subsequent growth. Following an appraisal of the techniques and their application, there is a short discussion and consideration for future opportunities.

Within the British nuclear inventory, waste is classified into three main categories, including Intermediate Level Waste (ILW). ILW mainly consists of fuel casing metallic swarf, where parts of uranium metal are also expected to have been agglomerated. ILW treatment route includes the material storage in stainless steel drums and subsequent grout encapsulation. The solidified matrix is believed to maintain the radioactive waste fully confined and immobile. Recent inspections revealed mechanical distortion around the steel liner in a proportion of the inspected drums. The distortion has been ascribed to the corrosion of the encapsulated metallic parts. The generated corrosion products occupy greater volume than the parent metal, resulting in an internal volume expansion which imposes stress/strain on the encapsulants. This study attempts to correlate the level of internal corrosion with the magnitude of package degradation in ILW drum–simulant systems by favouring the use of powerful synchrotron X-rays.

The reaction of unirradiated-U with liquid water under deuterium overpressure was studied by conducting nine separate reactions at different temperatures. Post-corrosion examination of the surfaces was conducted using FIB, SIMS and XRD. Measurements of the reacting-water pH and sample degassing were made after the experiments were stopped. Isotopic labelling allowed better investigation of the mechanisms occurring in this system. The analyses showed that bulk-UH3 forms at the metal-oxide interface. The observed gas evolution reduction in the headspace was attributed to gas suppression of hydrogen generated through oxidation, and not D2 gas migration through the water. This suppression facilitates UH3 formation.

The series of experiments described in this report was conducted to demonstrate the (expected) difference in the gas flow behaviour of sintered steel filters that had been manipulated to simulate possible fault scenarios. The filters used in this work are similar to the ones that will be installed on the Self Shielded Box (SSB). For that reason, an experimental gas rig was constructed to allow the filter behaviour to be examined using three different test methods. Six filter conditions were used (holed (2.8 mm), pinholed (10 x 0.3 mm), pristine, 0.25 blocked, 0.5 blocked and 0.75 blocked). All three scenarios have shown distinct differences between the various filters, successfully demonstrating their divergence in performance based on the filter condition and indicating the practicality of developing these ideas for industrial use, to monitor the condition of in-service filters.

This study describes the construction of highly-sensitive photo-electrochemical (PEC) immunosensor for the detection of neuron-specific enolase (NSE). The biosensing platform is comprised of photo-active NiWO4 nanostructures, in-situ-grown over a conductive substrate (indium tin oxide) using a low-temperature template-based co-precipitation approach. The discussed approach enables the formation of discrete, yet morphologically-analogous, nanostructures with complete coverage (pinhole-free) of the electrode surface. The in-situ-grown nanostructure possess dense population with sharp saw-blade like morphological features that can support substantial immobilisation of anti-NSE agent. The constructed platform demonstrated excellent photo-catalytic activity towards uric acid (UA) which served as the base for the Electrochemical -mechanism (EC) based PEC inhibition sensing. The detection of NSE, relied on its obstruction in analytical signal observed for the photo-oxidation of UA after binding to the electrode surface via protein-antibody interaction. The constructed PEC immunosensor exhibits signal sensitivity up to 0.12 ng mL(-1) of NSE with excellent signal reproducibility and electrode replicability. Moreover, the constructed platform was successfully used for NSE determination in human serum samples.

The study explores carbon quantum dots (C-dots) as potential candidates for enhancing the signal sensitivity of an electrochemical sensor devised for biologically important molecule, such as uric acid (UA). The C-dots were evaluated for their electrochemical characteristics in combination with Fe3O4 nanoparticles (Fe3O4 NPs), which were applied as the primary electro-catalytic promoter. The hybrid nanocomposite (C-dots/Fe3O4 HCs) formation was achieved by facilitating the adsorption of C-dots over Fe3O4 NPs using amine-carbonyl interactions. Unlike, one pot method, the proposed strategy enables aggregation-free coverage of Fe3O4 NPs with highly conductive layer of C-dots that can act as conduction centres to support ultra-fast electron transfer kinetics to satisfy the need of high signal sensitivity. The hybrid composite demonstrated remarkable signal improvement when tested against the electrochemical oxidation of UA. The heighten current response and lower over-potential values enabled development of a DC-amperometric (DC-AMP) sensor for UA with a linear working range of 0.01 to 0.145 mu M and signal sensitivity measurable up to 6.0 x 10(-9) M. The said improvement was manifested as a synergetic outcome of active redox couple (Fe (III/II)), larger surface area of Fe3O4 NPs engulfed with a layer of highly conductive C-dots acting as efficient charge sensitisers.

Here we report the results of multiple analytical techniques on sub-mm particulate material derived from Unit 1 of the Fukushima Daiichi Nuclear Power Plant to provide a better understanding of the events that occurred and the environmental legacy. Through combined x-ray fluorescence and absorption contrast micro-focused x-ray tomography, entrapped U particulate are observed to exist around the exterior circumference of the highly porous Si-based particle. Further synchrotron radiation analysis of a number of these entrapped particles shows them to exist as UO2-identical to reactor fuel, with confirmation of their nuclear origin shown via mass spectrometry analysis. While unlikely to represent an environmental or health hazard, such assertions would likely change should break-up of the Si-containing bulk particle occur. However, more important to the long-term decommissioning of the reactors at the FDNPP (and environmental clean-upon), is the knowledge that core integrity of reactor Unit 1 was compromised with nuclear material existing outside of the reactors primary containment.

The reaction of unirradiated-U with liquid water was investigated under initial vacuum-contained conditions. Ten samples were examined at varying temperatures and reaction times. Post-corrosion examination of the surfaces was conducted using FIB, SIMS and XRD. Measurements of the reacting water pH and degassing of the samples was conducted after the reaction was stopped. From the analyses, it was concluded that bulk-UH3 formation occurred on the majority of the samples. It is suggested that UH3 formation was facilitated by a critical 'threshold' headspace pressure similar to 0.5bar over which pressure deficiency is observed in the free headspace.