Recyclable copper catalysts based on imidazolium-tagged bis(oxazolines): A marked enhancement in rate and enantioselectivity for Diels-Alder reactions in ionic liquid

Imidazolium-tagged bis(oxazolines) have been prepared and used as chiral ligands in the copper(II)-catalysed Diels-Alder reaction of N-acryloyl- and N-crotonoyloxazolidinones with cyclopentadiene and 1,3-cyclohexadiene in the ionic liquid 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [emim][NTf2]. A significant and substantial enhancement in the rate and enantioselectivity was achieved in [emim][NTf2] compared with dichloromethane. For example, complete conversion and enantioselectivities up to 95 % were obtained for the reaction between N-acryloyloxazolidinone and cyclopentadiene within 2 min in [emim][NTf2] whereas the corresponding reaction in dichloromethane required 60 min to reach completion and gave an ee of only 16 %. The enhanced rates obtained in the ionic liquid enabled a catalyst loading as low as 0.5 mol % to give complete conversion within 2 min while retaining the same level of enantioselectivity. The imidazolium-tagged catalysts can be recycled ten times without any loss in activity or enantioselectivity and showed much higher affinity for the ionic liquid phase during the recycle procedure than the analogous uncharged ligand.

Temperature and strain rate dependence of syntactic foam under tensile and shear loads

The behaviour of syntactic foam is strongly dependent on temperature and strain rate. This research focuses on the behaviour of syntactic foam made of epoxy and glass microballoons in the glassy, transition and rubbery regions. Both epoxy and epoxy foam are investigated separately under tension and shear loadings in order to study the strain rate and temperature effects. The results indicate that the strength and strain to failure data can be collapsed onto master curves depending on temperature reduced strain rate. The highest strain to failure occurs in the transition zone. The presence of glass microballoons reduces the strain to failure over the entire range considered, an effect that is particularly significant under tensile loading. However, as the microballoons increase the elastic modulus significantly in the rubbery zone but reduce it somewhat in the glassy zone, the effect on the strength is more complicated. Different failure mechanisms are identified over the temperature-frequency range considered. As the temperature reduced strain rate is decreased, the failure mechanism changes from microballoon fracture to matrix fracture and debonding between the matrix and microballoons. © IMechE 2012.

Influence of micro and macro cracks due to sustained loading on chloride-induced corrosion of reinforced concrete beams

Chloride-induced corrosion of steel is one of the most commonly found problems affecting the durability of reinforced concrete structures in both marine environment and where de-icing salt is used in winter. As the significance of micro-cracks on chloride induced corrosion is not well documented, 24 reinforced concrete beams (4 different mixes - one containing Portland cement and another containing 35% ground granulated blastfurnace slag at 0.45 and 0.65 water-binder ratios) were subjected to three levels of sustained lateral loading (0%, 50% and 100% of the load that can induce 0.1 mm wide cracks on the tension surface of beam - F_0.1) in this work. The beams were then subjected to weekly cycles of wetting with 10% NaCl solution for 1 day followed by 6 days of drying at 20 (±1) °C up to an exposure period of 60 weeks. The progress of corrosion of steel was monitored using half-cell potential apparatus and linear polarisation resistance (LPR) test. These results have shown that macro-cracks (at load F_0.1) and micro-cracks (at 50% of F_0.1) greatly accelerated both the initiation and propagation stages of the corrosion of steel in the concrete beams. Lager crack widths for the F_0.1 load cases caused higher corrosion rates initially, but after about 38 weeks of exposure, there was a decrease in the rate of corrosion. However, such trends could not be found in 50% F _0.1 group of beams. The extent of chloride ingress also was influenced by the load level. These findings suggest that the effect of micro-cracking at lower loads are very important for deciding the service life of reinforced concrete structures in chloride exposure environments. © 2014 4th International Conference on the Durability of Concrete Structures.

Crush responses of composite cylinder under quasi-static and dynamic loading

Despite the abundance of studies investigating the performance of composite structures under crush loading, disagreement remains in the literature regarding the effect of increased strain rate on the crush response. This study reports an experimental investigation of the behaviour of a carbon-epoxy composite energy absorber under static and dynamic loading with a strain rate of up to 100s^-1. Consistent damage modes and measured force responses were obtained in samples tested under the same strain rate. The energy absorption was found to be independent of strain rate as the total energy absorption appeared to be largely associated with fibre-dominated fracture, which is independent of strain rate within the studied range. The results from this study are beneficial for the design of energy absorbing structures.

Effect of cooling rate on the properties of high density polyethylene/multi-walled carbon nanotube composites

High density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt mixing using twin-screw extrusion. The extruded pellets were compression moulded at 200°C for 5min followed by cooling at different cooling rates (20°C/min and 300°C/min respectively) to produce sheets for characterization. Scanning electron microscopy (SEM) shows that the MWCNTs are uniformly dispersed in the HDPE. At 4 wt% addition of MWCNTs composite modulus increased by over 110% compared with the unfilled HDPE (regardless of the cooling rate). The yield strength of both unfilled and filled HDPE decreased after rapid cooling by about 10% due to a lower crystallinity and imperfect crystallites. The electrical percolation threshold of composites, irrespective of the cooling rate, is between a MWCNT concentration of 1∼2 wt%. Interestingly, the electrical resistivity of the rapidly cooled composite with 2 wt% MWCNTs is lower than that of the slowly cooled composites with the same MWCNT loading. This may be due to the lower crystallinity and smaller crystallites facilitating the formation of conductive pathways. This result may have significant implications for both process control and the tailoring of electrical conductivity in the manufacture of conductive HDPE/MWCNT nanocomposites.

FRP-to-concrete bond-slip behaviour under dynamic loading

Strengthening reinforced concrete (RC) structures by externally bonded FRP composites has been widely used for static loading and seismic retrofitting since 1990s. More recently many studies on strengthening concrete and masonry structures with externally bonded FRP for improved blast and impact resistance in protective engineering have also been conducted. The bond behaviour between the FRP and concrete plays a critical role in a strengthening system with externally bonded FRP. However, the understanding of how the bond between FRP and concrete performs under high strain rate is severely limited. Due to the dynamic characteristics of blast and impact loading, the bond behaviour between FRP and concrete under such loading is very different from that under static loading. This paper presents a study on the dynamic bond-slip behaviour based on both the numerical analysis and test results. A dynamic bond-slip model is proposed in this paper.

Estimation of the small strain stiffness of glacial till using geophysical methods and barometric loading response

Stiffness values in geotechnical structures can range over many orders of magnitude for relatively small operational strains. The typical strain levels where soil stiffness changes most dramatically is in the range 0.01-0.1%, however soils do not exhibit linear stress-strain behaviour at small strains. Knowledge of the in situ stiffness at small strain is important in geotechnical numerical modelling and design. The stress-strain regime of cut slopes is complex, as we have different principle stress directions at different positions along the potential failure plane. For example, loading may be primarily in extension near the toe of the slope, while compressive loading is predominant at the crest of a slope. Cuttings in heavily overconsolidated clays are known to be susceptible to progressive failure and subsequent strain softening, in which progressive yielding propagates from the toe towards the crest of the slope over time. In order to gain a better understanding of the rate of softening it would be advantageous to measure changes in small strain stiffness in the field.

Biological phosphorus removal during high-rate, low-temperature, anaerobic digestion of wastewater.

We report, for the first time, extensive biologically-mediated phosphate removal from wastewater during high-rate anaerobic digestion (AD). A hybrid sludge bed/fixed-film (packed pumice stone) reactor was employed for low-temperature (12°C) anaerobic treatment of synthetic sewage wastewater. Successful phosphate removal from the wastewater (up to 78% of influent phosphate) was observed, mediated by biofilms in the reactor. Scanning electron microscopy and energy dispersive X-ray analysis revealed the accumulation of elemental phosphorus (~2%) within the sludge bed and fixed-film biofilms. 4’, 6-diamidino-2-phenylindole (DAPI) staining indicated phosphorus accumulation was biological in nature and mediated through the formation of intracellular inorganic polyphosphate (polyP) granules within these biofilms. DAPI staining further indicated that polyP accumulation was rarely associated with free cells. Efficient and consistent chemical oxygen demand (COD) removal was recorded, throughout the 732-day trial, at applied organic loading rates between 0.4-1.5 kg COD m-3 d-1 and hydraulic retention times of 8-24 hours, while phosphate removal efficiency ranged from 28-78% on average per phase. Analysis of protein hydrolysis kinetics and the methanogenic activity profiles of the biomass revealed the development, at 12˚C, of active hydrolytic and methanogenic populations. Temporal microbial changes were monitored using Illumina Miseq analysis of bacterial and archaeal 16S rRNA gene sequences. The dominant bacterial phyla present in the biomass at the conclusion of the trial were the Proteobacteria and Firmicutes and the dominant archaeal genus was Methanosaeta. Trichococcus and Flavobacterium populations, previously associated with low temperature protein degradation, developed in the reactor biomass. The presence of previously characterised polyphosphate accumulating organisms (PAOs) such as Rhodocyclus, Chromatiales, Actinobacter and Acinetobacter was recorded at low numbers. However, it is unknown as yet if these were responsible for the luxury polyP uptake observed in this system. The possibility of efficient phosphate removal and recovery from wastewater during AD would represent a major advance in the scope for widespread application of anaerobic wastewater treatment technologies.

A straightforward method to obtain the cohesive laws of bonded joints under mode I loading

A simple procedure to measure the cohesive laws of bonded joints under mode I loading using the double cantilever beam test is proposed. The method only requires recording the applied load–displacement data and measuring the crack opening displacement at its tip in the course of the experimental test. The strain energy release rate is obtained by a procedure involving the Timoshenko beam theory, the specimen’s compliance and the crack equivalent concept. Following the proposed approach the influence of the fracture process zone is taken into account which is fundamental for an accurate estimation of the failure process details. The cohesive law is obtained by differentiation of the strain energy release rate as a function of the crack opening displacement. The model was validated numerically considering three representative cohesive laws. Numerical simulations using finite element analysis including cohesive zone modeling were performed. The good agreement between the inputted and resulting laws for all the cases considered validates the model. An experimental confirmation was also performed by comparing the numerical and experimental load–displacement curves. The numerical load–displacement curves were obtained by adjusting typical cohesive laws to the ones measured experimentally following the proposed approach and using finite element analysis including cohesive zone modeling. Once again, good agreement was obtained in the comparisons thus demonstrating the good performance of the proposed methodology.

Cardiovascular effects of a medetomidine constant rate infusion at different dose levels in anaesthetized dogs

Les effets cardiovasculaires des alpha-2 agonistes, particulièrement importants chez les chiens, limitent leur utilisation en pratique vétérinaire. La perfusion à débit constant (PDC) de ces drogues, comme la médétomidine (MED) permettrait un contrôle plus précis de ces effets. Les effets hémodynamiques de plusieurs doses de MED en PDC ont été évalués chez le chien. Lors de cette étude prospective, réalisée en double aveugle, 24 chiens en santé, ont reçu de façon aléatoire une des 6 doses de MED PDC (4 chiens par groupe). Les chiens ont été ventilés mécaniquement pendant une anesthésie minimale standardisée avec de l’isoflurane dans de l’oxygène. Une dose de charge (DC) de médétomidine a été administrée aux doses de 0.2, 0.5, 1.0, 1.7, 4.0 ou 12.0 µg/kg pendant 10 minutes, après laquelle la MED PDC a été injectée à une dose identique à celle de la DC pendant 60 minutes. L’isoflurane a été administré seul pendant une heure après l’administration d’une combinaison d’ISO et de MED PDC pendant 70 minutes. La fréquence cardiaque (FC), la pression artérielle moyenne (PAM) et l’index du débit cardiaque (IC) ont été mesurés. Des prélèvements sanguins ont permis d’évaluer le profil pharmacocinétique. D’après ces études, les effets hémodynamiques de la MED PDC pendant une anesthésie à l’isoflurane ont été doses-dépendants. L’IC a diminué progressivement alors que la dose de MED augmentait avec: 14.9 (12.7), 21.7 (17.9), 27.1 (13.2), 44.2 (9.7), 47.9 (8.1), and 61.2 (14.1) % respectivement. Les quatre doses les plus basses n’ont provoqué que des changements minimes et transitoires de la FC, de la PAM et de l’IC. La pharmacocinétique apparaît clairement dose-dépendante. De nouvelles expériences seront nécessaires afin d’étudier l’utilisation clinique de la MED PDC.

Sparse polynomial approximation in positive order Sobolev spaces with bounded mixed derivatives and applications to elliptic problems with random loading

In the present paper we study the approximation of functions with bounded mixed derivatives by sparse tensor product polynomials in positive order tensor product Sobolev spaces. We introduce a new sparse polynomial approximation operator which exhibits optimal convergence properties in L2 and tensorized View the MathML source simultaneously on a standard k-dimensional cube. In the special case k=2 the suggested approximation operator is also optimal in L2 and tensorized H1 (without essential boundary conditions). This allows to construct an optimal sparse p-version FEM with sparse piecewise continuous polynomial splines, reducing the number of unknowns from O(p2), needed for the full tensor product computation, to View the MathML source, required for the suggested sparse technique, preserving the same optimal convergence rate in terms of p. We apply this result to an elliptic differential equation and an elliptic integral equation with random loading and compute the covariances of the solutions with View the MathML source unknowns. Several numerical examples support the theoretical estimates.

Effect of temperature and strain rate on the compressive behaviour of supramolecular polyurethane

Supramolecular polyurethanes (SPUs) possess thermoresponsive and thermoreversible properties, and those characteristics are highly desirable in both bulk commodity and value-added applications such as adhesives, shape-memory materials, healable coatings and lightweight, impact-resistant structures (e.g. protection for mobile electronics). A better understanding of the mechanical properties, especially the rate and temperature sensitivity, of these materials are required to assess their suitability for different applications. In this paper, a newly developed SPU with tuneable thermal properties was studied, and the response of this SPU to compressive loading over strain rates from 10−3 to 104 s−1 was presented. Furthermore, the effect of temperature on the mechanical response was also demonstrated. The sample was tested using an Instron mechanical testing machine for quasi-static loading, a home-made hydraulic system for moderate rates and a traditional split Hopkinson pressure bars (SHPBs) for high strain rates. Results showed that the compression stress-strain behaviour was affected significantly by the thermoresponsive nature of SPU, but that, as expected for polymeric materials, the general trends of the temperature and the rate dependence mirror each other. However, this behaviour is more complicated than observed for many other polymeric materials, as a result of the richer range of transitions that influence the behaviour over the range of temperatures and strain rates tested.

Success rate of immediate nonfunctional loaded single-tooth implants: Immediate versus delayed implantation

Purpose: The aim of this study was to evaluate the success rate of maxillary immediate nonfunctional single-tooth loaded implants used into fresh extraction sites (immediate placement condition) or healed ridge (delayed placement condition).Materials and Methods: Eighty-two dental implants were placed in the maxilla of 64 consecutive patients from Private practice office and from a specialization course in Implantology. Forty-six implants were inserted under immediate placement condition, and 36 were inserted under delayed placement condition. The criteria used to evaluate success rate were those previously described by Albrektsson and Zarb (Int J Prosthodont 1993;6: 95-105), and follow-up period ranged from 18.0 to 39.7 months.Results: Seventy-nine implants fulfilled the success rate criteria (96.3%). Moreover, differences concerning implantation condition were not significant (P = 0.33, Qui-square test): three of the failed implants were from immediate placement group (success rate of 93.5%), and none was from delayed placement group (success rate of 100.0%).Conclusion: In the present sample, no statistically significant differences were detected for immediate nonfunctional single-tooth loaded implants under immediate placement condition in comparison with those inserted under delayed placement condition; both protocols had high success rate in maxillary incisors, canines, and premolars areas.

Early loading of single crowns supported by 6-mm-long implants with a moderately rough surface: a prospective 2-year follow-up cohort study

AimTo evaluate prospectively the clinical and radiographic outcomes after 2 years of loading of 6 mm long moderately rough implants supporting single crowns in the posterior regions.Material and methodsForty SLActive Straumann (R) short (6 mm) implants were placed in 35 consecutively treated patients. Nineteen implants, 4.1 mm in diameter, and 21 implants, 4.8 mm in diameter, were installed. Implants were loaded after 6 weeks of healing. Implant survival rate, marginal bone loss and resonance frequency analysis (RFA) were evaluated at different intervals. The clinical crown/implant ratio was also calculated.ResultsTwo out of 40 implants were lost before loading. Hence, the survival rate before loading was 95%. No further technical or biological complications were encountered during the 2-year follow-up. The mean marginal bone loss before loading was 0.34 +/- 0.38 mm. After loading, the mean marginal bone loss was 0.23 +/- 0.33 and 0.21 +/- 0.39 mm at the 1- and 2-year follow-ups. The RFA values increased between insertion (70.2 +/- 9) and the 6-week evaluation (74.8 +/- 6.1). The clinical crown/implant ratio increased with time from 1.5 at the delivery of the prosthesis to 1.8 after 2 years of loading.ConclusionShort implants (6 mm) with a moderately rough surface loaded early (after 6 weeks) during healing yielded high implant survival rates and moderate loss of bone after 2 years of loading. Longer observation periods are needed to draw more definite conclusions on the reliability of short implants supporting single crowns.To cite this article:Rossi F, Ricci E, Marchetti C, Lang NP, Botticelli D. Early loading of single crowns supported by 6-mm-long implants with a moderately rough surface: a prospective 2-year follow-up cohort study.Clin. Oral Impl. Res. 21, 2010; 937-943.doi: 10.1111/j.1600-0501.2010.01942.x.

Survival rate of osseointegrated implants in atrophic maxillae grafted with calvarial bone: a retrospective study

The aim of this study was to evaluate the clinical survival rate of osseointegrated implants placed in the atrophic maxilla that has been reconstructed by means of autogenous bone grafts harvested from a cranial calvarial site. Further, we sought to analyse the level of pen-implant bone after prosthetic rehabilitation and to determine subjective patient satisfaction with the treatment performed. This study conformed to the STROBE guidelines regarding retrospective studies. Twenty-five patients who had received osseointegrated implants with late loading in the reconstructed atrophic maxilla were included in the study. The survival rate and level of pen-implant bone loss were evaluated. A questionnaire related to the surgical and prosthetic procedures was completed. The observed implant survival rate was 92.35%. The mean bone loss recorded was 1.76 mm in the maxilla and 1.54 mm in the mandible. The results of the questionnaire indicated a high level of patient satisfaction, little surgical discomfort, and that the patients would recommend the procedure and would undergo the treatment again. From the results obtained, it is concluded that the cranial calvarial site is an excellent donor area; calvarial grafts provided stability and maintenance of bone volume over the course of up to 11 years.