A comparison of long and short versions of the oral health impact profile in an edentulous population

Abstract no. 215published_or_final_versio

Impact of oral disease among the elderly in Hong Kong

published_or_final_versio

Photocatalytic water disinfection by simple and low-cost monolithic and heterojunction ceramic wafers

In this work, the photocatalytic disinfection of Escherichia coli (E. coli) using dual layer ceramic wafers, prepared by a simple and low-cost technique, was investigated. Heterojunction wafers were prepared by pressing TiO2 and WO3 powders together into 2 layers within a single, self-supported monolith. Data modelling showed that the heterojunction wafers were able to sustain the formation of charged species (after an initial "charging" period). In comparison, a wafer made from pure TiO2 showed a less desirable bacterial inactivation profile in that the rate decreased with time (after being faster initially). The more favourable kinetics of the dual layer system was due to superior electron-hole vectorial charge separation and an accumulation of charges beyond the initial illumination period. The results demonstrate the potential for developing simplified photocatalytic devices for rapid water disinfection

Nanomechanical and structural properties of native cellulose under compressive stress

Cellulose is an important biopolymer with applications ranging from its use as an additive in pharmaceutical products to the development of novel smart materials. This wide applicability arises in part from its interesting mechanical properties. Here we report on the use of high pressure X-ray diffraction and Raman spectroscopy in a diamond anvil cell to determine the bulk and local elastic moduli of native cellulose. The modulus values obtained are 20 GPa for the bulk modulus and 200-355 and 15 GPa for the crystalline parts and the overall elastic (Young's) modulus, respectively. These values are consistent with those calculated from tensile measurements. Above 8 GPa, the packing of the cellulose chains within the fibers undergoes significant structural distortion, whereas the chains themselves remain largely unaffected by compression

Decoupling polymer, water and ion transport dynamics in ion-selective membranes for fuel cell applications

Ion conducting polymer membranes are designed for applications ranging from separation and dialysis, to energy conversion and storage technologies. A key application is in fuel cells, where the semi-permeable polymer membrane plays several roles. In a fuel cell, electrical power is generated from the electrochemical reaction between oxygen and hydrogen, catalysed by metal nanoparticles at the cathode and anode sites. The polymer membrane permits the selective transport of H+ or OH− to enable completion of the electrode half-reactions, plays a major role in the management of water that is necessary for the conduction process and is a product in the reactions, and provides a physical barrier against leakage across the cell. All of these functions must be optimised to enable high conduction efficiency under operational conditions, including high temperatures and aggressive chemical environments, while ensuring a long lifetime of the fuel cell. Polymer electrolyte membranes used in current devices only partially meet these stringent requirements, with ongoing research to assess and develop improved membranes for a more efficient operation and to help realise the transition to a hydrogen-fuelled energy economy. A key fundamental issue to achieving these goals is the need to understand and control the nature of the strongly coupled dynamical processes involving the polymer, water and ions, and their relationship to the conductivity, as a function of temperature and other environmental conditions. This can be achieved by using techniques that give access to information across a wide range of timescales. Given the complexity of the dynamical map in these systems, unravelling and disentangling the various processes involved can be accessed by applying the “serial decoupling” approach introduced by Angell and co-workers for ion-conducting glasses and polymers. Here we introduce this concept and propose how it can be applied to proton- and anion-conducting fuel cell membranes using two main classes of these materials as examples

High-pressure synthesis and structural behavior of sodium orthonitrate Na3NO4

Sodium orthonitrate (Na3NO4) is an unusual phase containing the first example of isolated tetrahedrally bonded NO43- groups. This compound was obtained originally by heating together mixtures of Na2O and NaNO3 for periods extending up to > 14 days in evacuated chambers. Considering the negative volume change between reactants and products, it was inferred that a high-pressure synthesis route might favor the formation of the Na3NO4 compound. We found that the recovered sample is likely to be a high-pressure polymorph, containing NO43- groups as evidenced by Raman spectroscopy. The high-pressure behavior of Na3NO4 was studied using Raman spectroscopy and synchrotron X-ray diffraction in a diamond anvil cell above 60 GPa. We found no evidence for major structural transformations, even following laser heating experiments carried out at high pressure, although broadening of the Raman peaks could indicate the onset of disordering at higher pressure

Identification of new pillared-layered carbon nitride materials at high pressure

The compression of the layered carbon nitride C6N9H3·HCl was studied experimentally and with density functional theory (DFT) methods. This material has a polytriazine imide structure with Cl(-) ions contained within C12N12 voids in the layers. The data indicate the onset of layer buckling accompanied by movement of the Cl(-) ions out of the planes beginning above 10-20 GPa followed by an abrupt change in the diffraction pattern and c axis spacing associated with formation of a new interlayer bonded phase. The transition pressure is calculated to be 47 GPa for the ideal structures. The new material has mixed sp(2)-sp(3) hybridization among the C and N atoms and it provides the first example of a pillared-layered carbon nitride material that combines the functional properties of the graphitic-like form with improved mechanical strength. Similar behavior is predicted to occur for Cl-free structures at lower pressures

Carbon nitride frameworks and dense crystalline polymorphs

We used ab initio random structure searching (AIRSS) to investigate polymorphism in C3N4 carbon nitride as a function of pressure. Our calculations reveal new framework structures, including a particularly stable chiral polymorph of space group P43212 containing mixed sp2 and sp3 bonding, that we have produced experimentally and recovered to ambient conditions. As pressure is increased a sequence of structures with fully sp3-bonded C atoms and three-fold-coordinated N atoms is predicted, culminating in a dense Pnma phase above 250 GPa. Beyond 650 GPa we find that C3N4 becomes unstable to decomposition into diamond and pyrite-structured CN2

Carbon nitride frameworks and dense crystalline polymorphs

We used ab initio random structure searching (AIRSS) to investigate polymorphism in C3N4 carbon nitride as a function of pressure. Our calculations reveal new framework structures, including a particularly stable chiral polymorph of space group P43212 containing mixed sp2 and sp3-bonding, that we have produced experimentally and recovered to ambient conditions. As pressure is increased a sequence of structures with fully sp3-bonded C atoms and three-fold coordinated N atoms is predicted, culminating in a dense Pnma phase above 250 GPa. Beyond 650 GPa we find that C3N4 becomes unstable to decomposition into diamond and pyrite-structured CN2.Engineering and Physical Sciences Research Council (EPSRC) (Grant IDs: EP/J017639/1, EP/G007489/2, EP/K013688/1, EP/K014560/1, EP/L01709/1), Royal Society (Wolfson Research Merit Award), Czech Science Foundation (Junior Grant (CAMs – 16-21151Y)), European Research Council (Starting Grant scheme (BEGMAT – 678462))This is the author accepted manuscript. The final version is available from the American Physical Society via http://dx.doi.org/10.1103/PhysRevB.94.09410

High-Pressure Annealing of a Prestructured Nanocrystalline Precursor to Obtain Tetragonal and Orthorhombic Polymorphs of Hf3N4

Transition metal nitrides containing metal ions in high oxidation states are a significant goal for the discovery of new families of semiconducting materials. Most metal nitride compounds prepared at high temperature and high pressure from the elements have metallic bonding. However amorphous or nanocrystalline compounds can be prepared via metal-organic chemistry routes giving rise to precursors with a high nitrogen:metal ratio. Using X-ray diffraction in parallel with high pressure laser heating in the diamond anvil cell this work highlights the possibility of retaining the composition and structure of a metastable nanocrystalline precursor under high pressure-temperature conditions. Specifically, a nanocrystalline Hf3N4 with a tetragonal defect-fluorite structure can be crystallized under high-P,T conditions. Increasing the pressure and temperature of crystallization leads to the formation of a fully recoverable orthorhombic (defect cottunite-structured) polymorph. This approach identifies a novel class of pathways to the synthesis of new crystalline nitrogen-rich transition metal nitrides