Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Strength and permeation properties as an indicator of durability of concrete

Durability of concrete is a great concern to all designers, owners and users of reinforced concrete structures. As a result, more restrictive regulations are being introduced in various Codes of Practice dealing with the design of these structures. Attempts are being made by various researchers to develop performance based specification. For this to be successful standard non destructive tests are required which will be used to assess the durability of concretes. In parallel with this approach, a research team in Queen’s University Belfast, U. K., investigated the effect of different mix parameters on workability, strength and various permeation properties. Furthermore, durability parameters such as freeze-thaw salt scaling resistance and carbonation depth were also investigated. The research was part funded by the Department of Environment, Transport and the Regions (DETR). This paper reports of the findings from this study. The results from this investigation showed that some of the non destructive tests used were reasonably well correlated with carbonation and freeze-thaw salt scaling resistance of CEM I concrete. If the mix parameters such as aggregate-cement ratio or water-cement ratio are known, better correlation can be obtained. Further investigation is required varying other mix parameters including various aggregates, admixtures and air entrainments before the result can be used for developing mix design methods for durable concretes. Also long term site tests are required to validate the results obtained from the accelerated laboratory tests used to study the carbonation resistance and freeze-thaw salt scaling resistance.

An investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues in silage effluent

The farm production of silage as a winter-feed supplement is widespread. However, the bins in which silage is produced are subject to acidic and microbial attacks. Both these types of attack can lead to a weakening and failure of the concretes, especially on the outer lip of the open side of the silage pit. Consequently, the development of an acid-resistant concrete that can extend the life span of silage bins on farms could lead to considerable cost savings for farmers and, hence, can improve farm productivity. This paper reports on test results of an investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues (Bauxsol™) exposed to sulphuric acid environments in the laboratory and to silage effluents. The concrete manufactured had a fixed water–cement ratio of 0.55 and natural sand was replaced with the Bauxsol™ at 0%, 5%, 10%, 15% and 20% by cement mass. Results indicated that the use of Bauxsol™ as a sand replacement material improved the behaviour of concrete both in sulphuric acid in the laboratory as well as in the silage effluent. Consequently, it is concluded that the Bauxsol™ can be used to replace 10% of natural sand to produce concrete that is resistant to silage effluents, providing an extended service life over conventional concretes used in silage pits.

Investigation of Ultimate Strength of Deck Slabs in Steel-Concrete Bridges

In the last 50 years, many bridges have been built as composite structures with decks of reinforced concrete that are supported by longitudinal steel beams. The presence of the longitudinal steel beams and the unloaded area of concrete slab cause the loaded deck slabs to be restrained against lateral expansion. As a result, a compressive membrane thrust is developed. In experimental tests, the authors built a series of one-third scale steel-concrete composite bridge models with several varying structural parameters, including concrete compressive strength, reinforcement percentage, and the size of steel supporting beams. After comparing the results of different models, the influence of these structural parameters on the amount of compressive membrane action in the deck slab was evaluated. Furthermore, the improvement of an existing theoretical model provided accurate predictions for the loading-carrying capacities.