Hydration of Portland cement with high replacement by siliceous fly ash

The effects of two different low calcium fly ashes on the hydration of ordinary Portland cement (OPC) pastes containing 50 wt.% of fly ash were investigated over a hydration time of 550 days. The results were compared with a reference blend of OPC containing 50 wt.% of inert quartz powder allowing the distinction between "filler effect" and pozzolanic reaction.Until 2 days, no evidence of fly ash reaction was measured and its influence on the hydration is mainly related to the “filler effect”. From 7 days on, the effects of the pozzolanic reaction were observed by the consumption of portlandite, the change of the pore solution chemistry, the formation of a presumably water-rich inner hydration product and the change of the C–S–H composition towards higher Al/Si ratio compared to the C–S–H of neat OPC. Additional strength due to the pozzolanic reaction developed after 28 days of hydration.     

Transition-metal-free oxidative coupling reactions for the formation of C-C and C-N bonds mediated by TEMPO and its derivatives

The application of nitroxides for the development of new synthetic methods and their implementation in polymer chemistry, material science and beyond is one of the major research topics in our laboratory in the institute of organic chemistry at the WWU Münster. This short review focuses on our recent progress towards nitroxide-based transition-metal-free oxidative coupling reactions. The demand for organic surrogates for transition metals in such transformations is in our eyes unquestionable, since environmental and economic issues have become progressively more important in recent years. For this purpose, the 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO) is shown to be a highly efficient oxidant for the homo- and cross-coupling of Grignard reagents. This powerful C-C bond forming strategy allows the generation of conjugated polymers from bifunctional Grignard reagents. Moreover, cross-coupling of alkynyl Grignard compounds and nitrones can be accomplished under aerobic atmosphere with catalytic amounts of TEMPO. It is also shown that TEMPO-derived N-oxoammonium salts can act as suitable oxidants for formation of C-N bonds between non-preactivated benzoxazoles and secondary amines under metal-free conditions.     

Evidence-based medicine: quality and comparability of clinical trials investigating the efficacy of prostaglandin F(2α) for the treatment of bovine endometritis

The objective of this study was to evaluate the quality and comparability of published literature, and to summarize the effect of prostaglandin F(2α) (PGF(2α)) for the treatment of endometritis. It has been postulated that there is a dearth of high-level evidence-based research results in veterinary medicine. Also, there is a marked variation in the quality of studies in veterinary and animal science. Post-partum uterine infections occur commonly in dairy cattle and are reported to have a negative impact on reproductive performance. A comprehensive literature search was conducted utilizing online databases revealing a total of 2723 references. After applying specific exclusion criteria, a total of 68 trials were eligible for further analysis. These articles were evaluated utilizing specific parameters listed in an evaluation form such as randomization and the involvement of control groups. The analysis revealed that more than half of the trials (51·5%) were at least 20 years old. Furthermore, we found that about one third (36·8%) of all trials were controlled and randomized, while 3 of those (4·4%) were also blinded. Of those trials which calculated a calving-to-conception interval (n=30), 50% of the authors claimed an improvement, which was statistically significant in 23·3% of the cases. We conclude that there is a wide discrepancy between research results investigating the efficacy of PGF(2α).     

Piezoelectric activity of (1-x)[0.35Bi(Mg1/2Ti1/2)O3-0.3BiFeO3-0.35BiScO3] - xPbTiO3 ceramics as a function of temperature

The piezoelectric and ferroelectric properties of ceramics in the (1-x)[0.35Bi(Mg_1/2Ti_1/2)O₃-0.3BiFeO₃-0.35BiScO₃] - xPbTiO₃ (0.46?≤?x?≤?0.50) solid solution have been studied as a function of temperature with a view to establishing their potential for commercial usage as high T_C actuators and sensors. The polarisation, unipolar and bipolar strain, piezoelectric coefficient d₃₃ and coupling factor k_p all increased with temperature consistent with softening of extrinsic and intrinsic contributions to piezoactivity as T_C is approached. Small signal d₃₃ and k_p increased from 328?pm/V and ~0.45 at room temperature to >1100?pm/V and ~0.5, respectively, until depoling occurred at ~400°C, illustrating a significant improvement in operating temperature over PZT (~200°C) and demonstrating great potential for high temperature sensor applications. Bipolar (bi) and unipolar (uni) measurements (large signal, d^* ₃₃) normally used to demonstrate potential for actuation, revealed extremely promising values, d^* _33(bi)?=?940?pm/V and d^* _33(uni)?=?600?pm/V, up to 180°C, the limit of the experimental apparatus.     

Protein–Protein Docking with Large-Scale Backbone Flexibility Using Coarse-Grained Monte-Carlo Simulations

Most of the protein–protein docking methods treat proteins as almost rigid objects. Only the side-chains flexibility is usually taken into account. The few approaches enabling docking with a flexible backbone typically work in two steps, in which the search for protein–protein orientations and structure flexibility are simulated separately. In this work, we propose a new straightforward approach for docking sampling. It consists of a single simulation step during which a protein undergoes large-scale backbone rearrangements, rotations, and translations. Simultaneously, the other protein exhibits small backbone fluctuations. Such extensive sampling was possible using the CABS coarse-grained protein model and Replica Exchange Monte Carlo dynamics at a reasonable computational cost. In our proof-of-concept simulations of 62 protein–protein complexes, we obtained acceptable quality models for a significant number of cases.     

Development of gallium gradients in three‐stage Cu(In,Ga)Se2 co‐evaporation processes

We use secondary‐ion mass spectrometry, X‐ray diffraction and scanning electron microscopy to investigate the development over time of compositional gradients in Cu(In,Ga)Se₂ thin films grown in three‐stage co‐evaporation processes and suggest a comprehensive model for the formation of the well‐known ‘notch’ structure. The model takes into account the need for compensating Cu diffusion by movement of group‐III ions in order to remain on the quasi‐binary tie line and indicates that the mobilities of In and Ga ions differ. Cu diffuses towards the back in the second stage and towards the front in the third, and this is the driving force for the movement of In and Ga. The [Ga]/[In + Ga] ratio then increases in the direction of the respective Cu movement because In has a higher mobility at process conditions than has Ga. Interdiffusion of In and Ga can be considerable in the (In,Ga)₂Se₃ film of the first stage, but seems largely to cease in Cu(In,Ga)Se₂ and shows no signs of being boosted by the presence of a Cu₂Se layer. Copyright © 2011 John Wiley & Sons, Ltd.     

Straight-forward control of the degree of micro-cavity effects in organic light-emitting diodes based on a thin striped metal layer

We investigated the control of micro-cavity (MC) effects in organic light-emitting diodes (OLEDs) with the introduction of a striped thin metal layer between the indium tin oxide (ITO) layer and the hole transporting layer (HTL). With an enhanced MC effect obtained through the inserted metal layer, the forward emission of the OLED became stronger and the angular distribution became more forward-directed, leading to a current efficiency (CE) that was nearly 1.45 times higher than that of the reference device without the inserted metal layer. The net CE of the OLEDs with a striped metal layer was found to be determined by the area-weighted average of the CE’s of full-cavity-enhanced OLEDs and non-cavity OLEDs. It was also observed that the trade-off between resonance enhancement in efficiency and angle-dependent color stability, often found problematic in MC-based OLEDs, could be mitigated in a straight-forward manner by changing the relative portion of the metal-covered area.     

Infrared study of the MoO3 doping efficiency in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP)

Electrochemical doping produces clear changes in the vibrational spectra of organic semiconductors as we show here for the system molybdenum oxide (MoO₃) doped into the charge transport material 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP). Based on density-functional theory (DFT) calculations of vibrational spectra, the new spectral features can be attributed to the CBP cation that forms as a result of electron transfer from CBP to MoO₃. The intensity of the new vibrational lines is a direct measure for the probability of charge transfer. MoO₃ agglomerating within the CBP matrix limits the active interface area between the two species. The appearance of a broad electronic transition in the infrared range indicates a new electronic structure at the interface compared to the individual components. The intensity of this electronic excitation serves as a measure for the interface area indicating a linear increase with MoO₃ concentration. Deposition onto cooled substrates results in smaller agglomerates, and thus yields a higher efficiency.     

Crystal Structure and Microwave Dielectric Properties of LiRE9(SiO4)6O2 Ceramics (RE = La,Pr, Nd,Sm, Eu,Gd, and Er)

The crystal structure and microwave dielectric properties of apatite‐type LiRE₉(SiO₄)₆O₂ ceramics (RE = La, Pr, Nd, Sm, Eu, Gd, and Er) have been investigated. The densification of lithium apatites has been greatly improved with the addition of 1 wt% LiF. Selected area electron diffraction and X‐ray diffraction (XRD) Rietveld analysis confirm that these compounds belong to the P6₃/m (No. 176) space group with hexagonal crystal symmetry. The porosity‐corrected relative permittivity was found to decrease with decreasing ionic polarizability of RE³⁺ ions. Relationships between the structural parameters and microwave dielectric properties have been examined. The observed variation in the quality factor of LiRE₉(SiO₄)₆O₂ + 1 wt% LiF ceramics (RE = La, Pr, and Nd) was correlated with average cation covalency (%). The temperature coefficient of resonant frequency was found to depend on the bond valence sum of cations. LiEr₉(SiO₄)₆O₂ + 1 wt% LiF ceramics showed good microwave dielectric properties with ε_r = 12.8, Q_u × f = 13000 GHz and τ_f = +17 ppm/°C. All the compositions showed low coefficient of thermal expansion with thermal conductivity in the range 1.3–2.8 W (m K)^?1.