• Optimization of anti-wear and anti-bacterial properties of beta TiNb alloy via controlling duty cycle in open-air laser nitriding

      Chang, Xianwen; Smith, Graham; Quinn, James; Carson, Louise; Chan, Chi-Wai; Lee, Seunghwan; Technical University of Denmark (Chang, Lee), University of Chester (Smith), Queens University Belfast (Quinn, Chan) (Elsevier, 2020-07-09)
      A multifunctional beta TiNb surface, featuring wear-resistant and antibacterial properties, was successfully created by means of open-air fibre laser nitriding. Beta TiNb alloy was selected in this study as it has low Young’s modulus, is highly biocompatible, and thus can be a promising prosthetic joint material. It is, however, necessary to overcome intrinsically weak mechanical properties and poor wear resistance of beta TiNb in order to cover the range of applications to loadbearing and/or shearing parts. To this end, open-air laser nitriding technique was employed. A control of single processing parameter, namely duty cycle (between 5% and 100%), led to substantially different structural and functional properties of the processed beta TiNb surfaces as analyzed by an array of analytical tools. The TiNb samples nitrided at the DC condition of 60% showed a most enhanced performance in terms of improving surface hardness, anti-friction, antiwear and anti-bacterial properties in comparison with other conditions. These findings are expected to be highly important and useful when TiNb alloys are considered as materials for hip/knee articular joint implants
    • Performance Comparison of Protonic and Sodium Phosphomolybdovanadate Polyoxoanion Catholytes Within a Chemically Regenerative Redox Cathode Polymer Electrolyte Fuel Cell

      Ward, David B.; Gunn, Natasha; Uwigena, Nadine; Davies, Trevor J.; University of Chester (Elsevier, 2017-11-23)
      The direct reduction of oxygen in conventional polymer electrolyte fuel cells (PEFCs) is seen by many researchers as a key challenge in PEFC development. Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells offer an alternative approach via the indirect reduction of oxygen, improving durability and reducing cost. These systems substitute gaseous oxygen for a liquid catalyst that is reduced at the cathode then oxidised in a regeneration vessel via air bubbling. A key component of a CRRC system is the liquid catalyst or catholyte. To date, phosphomolybdovanadium polyoxometalates with empirical formula H3+nPVnMo12-nO40 have shown the most promise for CRRC PEFC systems. In this work, four catholyte formulations are studied and compared against each other. The catholytes vary in vanadium content, pH and counter ion, with empirical formulas H6PV3Mo9O40, H7PV4Mo8O40, Na3H3PV3Mo9O40 and Na4H3PV4Mo8O40. Thermodynamic properties, cell performance and regeneration rates are measured, generating new insights into how formulation chemistry affects the components of a CRRC system. The results include the best CRRC PEFC performance reported to date, with noticeable advantages over conventional PEFCs. The optimum catholyte formulation is then determined via steady state tests, the results of which will guide further optimization of the catholyte formulation.
    • A promising laser nitriding method for the design of next generation orthopaedic implants: Cytotoxicity and antibacterial performance of titanium nitride (TiN) wear nano-particles, and enhanced wear properties of laser-nitrided Ti6Al4V surfaces

      Chan, Chi Wai; Quinn, James; Hussain, Issam; Carson, Louise; Smith, Graham; Lee, Seunghwan; Queen's University Belfast; University of Lincoln; University of Chester; Technical University of Denmark
      In this study, fibre laser nitriding in open air was applied to the Ti6Al4V alloy in order to improve the wear resistance, thus minimising the generation of wear debris from the surfaces for load-bearing applications. The recent technological advancement to perform the laser nitriding process in open air allows the opportunity to surface-harden any curved and/or specific areas in the hip implants. The laser nitriding process was modulated between the pulsed mode and continuous wave (CW) mode by varying the duty cycle between 60% (pulsed) and 100% (CW). Our experimental investigations were divided into two stages in sequential order: Firstly, to create crack-free, homogenous and golden laser-nitrided surfaces by the proper selection of duty cycle. Secondly, it was to analyse the properties (both physical and chemical) of the wear debris as well as to evaluate their cytotoxicity and antibacterial performance. The laser-nitrided surfaces were characterised and tested using a variety of techniques, incl. optical microscopy, SEM-EDX, XRD, surface roughness and Vickers hardness measurements, as well as tribological tests (i.e. ball-on-disk wear tests and DLS). The wear debris from the laser-nitrided surfaces (collected in the wear tests) were analysed using TEM, XPS and SEM-EDX. Their toxicity was evaluated using in-vitro cell culture with macrophages at two time points (24 h and 48 h). The antibacterial performance was tested in vitro against two of the most commonly implicated pathogens in orthopaedic infection, namely Staphylococcus aureus and Escherichia coli for 24 h. Our findings indicated that the wear resistance of the surfaces after laser nitriding was significantly improved and the amount of wear debris generated was also significantly reduced. The wear particles from the laser-nitrided surfaces were in the nano-sized scale range (0.01 µm to 0.04 µm or 10 nm to 40 nm). They were found to be less toxic towards RAW264.7 macrophages, yet display antimicrobial properties against Staphylococcus aureus, when compared with the larger particles (1.5 µm in size) from the untreated surfaces. It is envisioned that successful fabrication of the non-toxic and highly wear-resistant TiN layer in Ti6Al4V using the open-air laser nitriding technique can enable progress towards the development of metal-on-metal (MoM) hip implants fully made of Ti-based alloys
    • Reverse microemulsion synthesis of layered gadolinium hydroxide

      Xu, Yadong; Suthar, Jugal; Egbu, Raphael; Weston, Andrew J.; Fogg, Andrew M.; Williams, Gareth R.; University College London; University of Chester (Elsevier, 2017-11-05)
      A reverse microemulsion approach has been explored for the synthesis of layered gadolinium hydroxide (LGdH) nanoparticles in this work. This method uses oleylamine as a multifunctional agent, acting as surfactant, oil phase and base. 1-butanol is additionally used as a co-surfactant. A systematic study of the key reaction parameters was undertaken, including the volume ratio of surfactant (oleylamine) to water, the reaction time, synthesis temperature, and the amount of co-surfactant (1-butanol) added. It proved possible to obtain pristine LGdH materials at temperatures of 120 °C or below with an oleylamine: water ratio of 1:4. Using larger amounts of surfactant or higher temperatures caused the formation of Gd(OH)3, either as the sole product or as a major impurity phase. The LGdH particles produced have sizes of ca. 200 nm, with this size being largely independent of temperature or reaction time. Adjusting the amount of 1-butanol co-surfactant added permits the size to be varied between 200 and 300 nm.
    • A single parameter approach to enhance the microstructural and mechanical properties of beta Ti-Nb alloy via open-air fiber laser nitriding

      Chan, Chi-Wai; Chang, Xianwen; Bozorgzadeh, Mohammad Amin; Smith, Graham C; Lee, Seunghwan; Queen's University Belfast, Technical University of Denmark, University of Chester (Elsevier, 2019-12-13)
      In this study, the idea of applying open-air laser nitriding to improve the microstructural and mechanical properties of beta Ti-45 at.% Nb alloy was demonstrated. Surface cracking after laser nitriding is one of the main reasons impeding direct translation of the laser nitriding technique from the laboratories to industries as cracks can be the weak points to initiate mechanical and corrosion failures in long-term usage. With proper selection of duty cycle (DC) between 40% (modulated mode) and 100% (continuous wave, CW mode) to control the laser energy input and laser-material-gas interaction time, the cracking problems of laser nitriding can be alleviated and even solved. A crack-free and uniformly gold-coloured nitrided surface was successfully obtained at the DC of 40% in this study. The morphology, microstructure, composition and mechanical properties of the nitrided samples were studied and analysed by optical microscopy (OM), scanning electron microscopy (SEM), SEM-energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and Vickers micro-hardness tests. The OM results indicated that minimum overlapping between the laser tracks would give desirable results to obtain the crack-free surface. The measurements from the SEM micrographs indicated the depth of the laser-nitrided areas ranged between 22 and 43 µm. The XRD findings showed that a clear conversion of the TiNb surface to a nitride as a result of laser nitriding was observed. The maximum hardness, as measured by the Vickers method in cross-sections, lay in the range of 780 to 870 HV after laser nitriding. To summarise, control of DC to obtain a crack free and quality surface via fiber laser nitriding in open air is a simpler and quicker approach in comparison with the conventional substrate preheating and nitrogen (N) dilution approaches. The single-parameter approach is more efficient than parameter optimisation via design of experiments (DOE) employed in conventional methods.
    • Understanding the impact of cavitation on hydrocarbons in the middle distillate range

      Price, Richard J.; Blazina, Damir; Smith, Graham C.; Davies, Trevor J.; Shell Global Solution ; Shell Global Solution ; University of Chester ; University of Chester (Elsevier, 2015-04-22)
      Hydrocarbons in the middle distillate range (C8 - C26) have been treated with ultrasound at 20 kHz - a frequency sufficient to drive acoustic cavitation. The high temperatures experienced as a result of the implosion of fuel vapour bubbles are sufficient to produce pyrolytic degradation and dehydrogenation, as well as a growth mechanism that results in the formation of small particles that have similarities with the primary soot particles produced during diesel combustion. These nanosized particles agglomerate as a result of kinetically driven collisions during cavitation to form a dispersion of micron sized particles in the treated hydrocarbon. The particles are carbonaceous in character, being a mixture of amorphous and graphitic-like carbon. The mass of material produced increases with the C/H atomic ratio of the hydrocarbon undergoing cavitation and is decreased through the addition (1 - 3 %v/v) of low boiling paraffinic hydrocarbons, possibly as a result of lowering the temperature developed inside imploding cavities. Dispersions of microparticles contain equilibrated levels of nanoparticles. If sufficiently high numbers of these smaller primary particles are present they agglomerate due to thermally driven collisions during post-cavitation storage. When this happened a sharp rise in the number of 1 - 2 µm particles was seen after only a few days. Some evidence is presented for the behaviour of ultrasonically treated hydrocarbons being related to the degradation of diesel fuel exposed to hydrodynamic cavitation in the fuel systems of modern common rail direct injection diesel engines.
    • Understanding the relationship between ignition delay and burn duration in a constant volume vessel at diesel engine conditions

      Davies, Trevor J.; University of Chester (Elsevier, 2014-06-19)
      Experiments were performed in a constant volume vessel, with fuel sprays injected into the vessel at various different pressure and temperature conditions chosen to represent diesel engine operation at various loads. A range of diesel primary reference fuels (i.e. mixtures of cetane and heptamethylnonane) of varying cetane number (CN) were tested, and as expected lower CN fuels have longer ignition delays. Burn period was plotted against ignition delay and two distinct trends can be seen: “mainly diffusion” diesel combustion in which burn period decreases with ignition delay and “mainly pre-mixed” diesel combustion in which burn period increases with ignition delay. There is typically a minimum in plots of burn period versus ignition delay which represents the transition between the two types of combustion mode. Higher CN, higher engine load and higher boost pressure would seem to favour “mainly diffusion” combustion whilst lower CN, lower loads and non boosted conditions favour “mainly pre-mixed” combustion.
    • The United Kingdom Ministry of Defence and the European Union's electrical and electronic equipment directives

      Powell-Turner, Julieanna; Antill, Peter; Fisher, Richard; Cranfield University
      The growth of the generation of Electrical and Electronic Equipment (EEE), and the use of hazardous substances in the production of these items, has required legislation to minimise the harm to the environment that their existing use, ultimate disposal and continued growth of the sector may pose. The European Union (EU) started to tackle this problem with the passing of two Directives in 2002, which focused on restricting the use of hazardous substances (RoHS - 2002/95/EC) and organising the recycling or disposal of discarded electronic and electrical equipment (WEEE - 2002/96/EC). These Directives have been recently recast and their scope widened; however, one exception to them remains items specifically designed for defence and military purposes. This paper looks at how and why these European Directives were passed, the impact they have had on defence in the United Kingdom (UK) up to the present moment, what impact the further extension of those directives might have on UK defence policy and how the UK Ministry of Defence (MOD) has begun to prepare for any extension, including the use of alternative products from the commercial market, and substituting less harmful materials. The paper reviews the information available to carry out future decision making and what level of decision making it can support. Where the data is insufficient, it makes recommendations on actions to take for improvement.
    • Using sub-micron silver-nanoparticle based films to counter biofilm formation by Gram-negative bacteria

      Gillett, Alice R.; Baxter, S. N.; Hodgson, Simon D.; Smith, Graham C.; Thomas, P. J.; University of Chester; Bangor University (Elsevier, 2018-02-16)
      Composite films comprised of silver nanoparticles (AgNPs) grown using a low-cost straightforward chemical bath based method have been deposited on glass microscope slides to investigate their potential as a sacrificial antibacterial coating. The as-deposited films have been characterised using scanning electron microscopy (SEM) and optical profilometry. These suggested that the films were relatively uniform in coverage. Chemical composition of the AgNP films has been studied by using x-ray photoelectron spectroscopy (XPS). The XPS analysis indicated that the Ag was in a metallic form able to sustain plasmon behaviour, and that low levels of residual nanoparticle precursors were present. Particle size was characterised using transmission electron microscopy (TEM) which showed an average particle size of 10.6 nm. The effectiveness of the films as an antibacterial coating was tested against Escherichia coli. The AgNP film was determined to be effective in the killing of E.coli cells over a 24 hour period when compared to equivalent samples that contained no silver. Of particular note was that only minimal bacterial growth was detected over the first 12 hours of testing, up to 78.6 times less than the control samples, suggesting the film is very efficient at slowing initial biofilm formation. The use of AgNP based films that have been synthesised using a novel low-cost, low-temperature and highly upscalable method is demonstrated as a promising solution for the deployment of silver as an effective sacrificial antimicrobial coating to counter the formation of potentially hazardous Gram negative biofilms.
    • Will Future Resource Demand Cause Significant and Unpredictable Dislocations for the UK Ministry of Defence?

      Antill, Peter; Powell-Turner, Julieanna; Cranfield University
      This paper focuses on the drivers which may affect future trends in material availability for defence, in particular, the availability of rare earth elements (REE). These drivers include resource concentration, tighter regulatory policy and its enforcement, export policies, their use in economic statecraft, increases in domestic demand, promoting greater efficiency in resource use, efforts to mitigate resource depletion and more efficient resource extraction while reducing its associated environmental impact. It looks at the effect these factors might have on global systems and supply chains, the impact on material insecurity and how this may exacerbate the issue of their use in UK military equipment. It finds that these drivers are likely to have an increasing impact on material availability (if measures are not taken to mitigate them), which will have consequences for the provision of military capability by the UK.
    • XPS Analysis of the chemical degradation of PTB7 polymers for organic photovoltaics

      Kettle, Jeff; Ding, Ziqian; Smith, Graham C.; Horie, Masaki; Bangor University, National Tsing Hua University, Taiwan, University of Chester (Elsevier, 2016-10-14)
      The chemical degradation of the Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] or ‘ PTB7’ has been studied using X-ray Photoelectron Spectroscopy (XPS). This material system appears to be intrinsically unstable especially when illuminated in air and XPS studies confirm the rapid photo-degradation is related to changes in chemical structure of the polymer. In particular, XPS spectra show an initial reduction in relative C-C intensity, suggests loss of the alkoxy side chains. This is followed by a dramatic increase in the level of oxygen-bonded species, especially C-O at ~286.5 eV and C(=O)O at 289.2 eV, indicative of COOH and OH group formation, and oxidation of S. The XPS results support the view that using processing additives reduces the chemical stability of the polymer and provides insight into strategies to improve molecular design to ensure higher chemical stability.