• Microinjection moulded polyetheretherketone biomaterials as spinal implants: physico-chemical and mechanical characterisation

      Tuinea-Bobe, Cristina-Luminita; Xia, H.; Ryabenkova, Yulia; Sweeney, John; Coates, Philip D.; Fei, G. (2019-03)
      Polyetheretherketone (or PEEK) is a thermoplastic polymer known for its high plasticity and toughness and has been widely employed as a material for a variety of load-bearing medical devices ranging from trauma implants to interspinal spacers and femoral stems. While being inherently chemically inert and therefore biocompatible and having very short lived post-radiation free radicals, PEEK presents different mechanical properties depending on its degree of crystallinity. It can be processed via extrusion, injection or compression moulding. However, these techniques do not allow high precision control over the fine morphological structure that strongly influences mechanical properties. Microinjection moulding, in contrast, makes it possible to produce fine details of medical implants with high precision and accuracy. Another advantage of this method is the controlled production of the material with heterogeneous structure due to variations in crystallinity. Having stiffness in the middle of the sample different from that at the edges enables a structure that mimics the bone/cartilage parts of an implant. This paper reports on the manufacturing of PEEK components by microinjection moulding, and their characterisation by physico-chemical (XRD, SAXS, TEM, FTIR, POM) and mechanical (tensile testing) means, in order to assess the suitability of use for biomedical application, such as spinal implants. We discuss the influence of such parameters as mould temperatures, injection speeds and hold pressures on the crystallinity and mechanical properties of the material.
    • Novel rhodium on carbon catalysts for the oxidation of benzyl alcohol to benzaldehyde: A study of the modification of metal/support interactions by acid pre-treatments

      Wilde, C.A.; Ryabenkova, Yulia; Firth, I.M.; Pratt, L.; Railton, J.; Bravo-Sanchez, M.; Sano, N.; Cumpson, P.J.; Coates, Philip D.; Liu, X.; et al. (2019-01-25)
      Rhodium nanoparticles or rhodium organometallic complexes are mainly used in catalysis for reduction or hydroformylation reactions. In this work instead, we explored the capabilities of Rh nanoparticles as an oxidation catalyst, applied to the oxidation of benzyl alcohol to benzaldehyde under very mild conditions (100 °C, and atmospheric pressure) as a model reaction. Here we report the preparation of novel Rh/C catalysts by using an impregnation protocol, with particular emphasis on the pre-treatment of the carbon supports by using HNO3 and HCl, as well as the characterization of these materials by using an array of methods involving TEM, XPS and XRPD. Our preparation method led to a wide Rh particle size distribution ranging from 20 to 100 nm, and we estimate an upper limit diameter of Rh nanoparticles for their activity towards benzyl alcohol oxidation to be ca. 30 nm. Furthermore, a HNO3 pre-treatment of the activated carbon support was able to induce a smaller and narrower particle size distribution of Rh nanoparticles, whereas a HCl pre-treatment had no effect or sintered the Rh nanoparticles. We rationalise these results by HNO3 as an acid able to create new nucleation sites for Rh on the carbon surface, with the final effect of smaller nanoparticles, whereas for HCl the effect of sintering was most likely due to site blocking of the nucleation sites over the carbon surface. The roles of acid centres on the carbon surfaces for the oxidation reaction was also investigated, and the larger their amounts the larger the amounts of by-products. However, by treatment with HNO3 we were able to convert neutral or basic carbons into supports capable to enhance the catalytic activity of Rh, and yet minimised detrimental effects on the selectivity of the oxidation to benzaldehyde.