Ultrasound‐activated Knoevenagel condensation of malononitrile with carbonylic compounds catalysed by alkaline‐doped saponites

α,β‐Unsaturated nitriles have been synthesized by Knoevenagel condensation of a carbonylic compound with malononitrile, assisted by sonochemical irradiation. Two alkaline‐promoted clays (Li⁺‐ and Cs⁺‐exchanged saponites) have been employed as catalysts. The influence of the carbonylic compound (benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic activity have been studied. Remarkable increase in the conversion values has been found when the reaction is activated by ultrasound, as compared with the thermal activation. In this green, solvent‐free procedure, α,β‐unsaturated nitriles have been produced in very high yields (97%) when the Cs⁺‐saponite is used as catalyst. Copyright © 2004 Society of Chemical Industry     

Investigation of texture effect on visual colour difference evaluation

The texture effect on visual colour difference evaluation was investigated in this study. Five colour centers were selected and textured colour pairs were generated using scanned textile woven fabrics and colour‐mapping technique. The textured and solid colour pairs were then displayed on a characterized cathode ray tube (CRT) monitor for colour difference evaluation. The colour difference values for the pairs with texture patterns are equal to 5.0 CIELAB units in lightness direction. The texture level was represented by the half‐width of histogram, which is called texture strength in this study. High correlation was found between texture strength and visual colour difference for textured colour pairs, which indicates that an increasing of 10 units of texture strength in luminance would cause a decreasing of 0.25 units visual difference for the five colour centers. The ratio of visual difference between textured and solid colour pairs also indicates a high parametric effect of texture. © 2005 Wiley Periodicals, Inc. Col Res Appl, 30, 341–347, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.     

Nutrient removal performance of an anaerobic–anoxic–aerobic process as a function of influent C/P ratio

The laboratory scale anaerobic–anoxic–aerobic (A²O) process fed with synthetic brewage wastewater was designed to investigate the effects of changing feed C/P ratio on the performance of biological nutrient removal (BNR) processes. In the experiment, the influent chemical oxygen demand (COD) concentration was kept at approximately 300 mg L^?1 while the total phosphorus concentration was varied to obtain the desired C/P ratio. Results showed that when the C/P ratio was lower than 32, phosphorus removal efficiency increased as C/P ratio increased linearly, while when the C/P ratio was higher than 32, the P removal efficiency was maintained at 90–98%, and effluent P concentration was lower than 0.5 mg L^?1. However, regardless of the C/P ratio, excellent COD removal (90% or higher) and good total nitrogen removal (75–84%) were maintained throughout the experiments. It was also found that very good linear correlation was obtained between COD uptake per unit P released in the anaerobic zone and C/P ratio. In addition, the P content in the wasted activated sludge increased with the decrease in the C/P ratio. Based on the results, it was recommended that the wastewater C/P ratio and its effects be incorporated into BNR design and operational procedures, appropriate C/P ratios were used to achieve the effluent treatment goals. Copyright © 2005 Society of Chemical Industry     

Effect of specimen size and loading conditions on spalling of concrete

Different qualities of concrete have been fire tested using different geometries of the specimens as well as different load levels and load configurations. The main objective with the study was to examine a test methodology consisting of a full‐scale test and different small scale‐tests for determining the probability of spalling and the amount of spalling of fire exposed concrete structures. A reference specimen was defined as a one‐sided fire exposed slab with the dimensions 1800 × 1200 mm² giving an exposed area of 1500 × 1200 mm². A number of concrete qualities with different probabilities for spalling, were tested using the reference specimen. These tests showed that the reference specimens worked well giving the expected test results. Small specimens were manufactured in different shapes with the same concrete as the one used in the reference tests. These small specimens were tested either at the same time as the reference specimens in the large furnace or afterwards on a small‐scale furnace where the fire exposed surface was 450 × 360 mm². The test results clearly show the increased probability and the increased amount of spalling by using external compressive loading. The results also show that by using pre‐stress through bars or wires the load can be lost due to heating of the bars/wires which results in a decreased amount of spalling. The boundary of the specimen also affects the amount of spalling. The spalling around the edges was in all tests less than the spalling on the central parts of the exposed area. It could also be noted that the spalling did not pass completely through any of the specimens. The reason for this is probably that the water/vapour could migrate out from the unexposed surface of the specimen. Copyright © 2006 John Wiley & Sons, Ltd.     

Biaxiale Ermüdung reibrührgeschweißter Strukturelemente

Biaxial fatigue of friction stir welded stiffened panels Within the framework of the European WelAir project, cruciform specimens made from stiffening FSW overlap joints were fatigued in the DLR biaxial test rig. To resemble the loading situation of pressurized fuselage structures, proportional loading without any phase shift, but with different load ratios λ between the loading components in both directions was applied.Natural crack initiation and subsequent crack growth were governed by the stiffness gradient caused by introducing the stringer. Cracks initiated and propagated at run‐in and run‐out locations in a direction perpendicular to the weld seam. The shortest fatigue life was observed for uniaxial loading in welding direction (λ = 0). An additional stress component perpendicular to the joint line (λ > 0) resulted in a higher number of cycles to failure. Similar to single stringer panels, increasing the load ratio also increased the number of cycles to failure for FSW clip‐stringer structural members, but additionally gives a different location of the fatal crack.     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Associative properties of perfluorooctyl end‐functionalized polystyrene–poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3‐tetrahydro‐perfluoroundecanoyl end‐functionalized polystyrene–poly(ethylene oxide) block (PS‐block‐PEO‐R_F) copolymers and their matching PS‐block‐PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and ¹⁹F NMR studies show that the PS‐block‐PEO copolymers, in contrast to their matching PS‐block‐PEO‐R_F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end‐functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS—and R_F—mediated micellization. Copyright © 2004 Society of Chemical Industry     

Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

Possibilities and extension of XRD material response analysis in failure research for the advanced evaluation of the damage level of Hertzian loaded components

Due to clearly distinguishable damage symptoms, it is differentiated between the surface and sub‐surface failure mode of rolling bearings. Material states red out by X‐ray diffraction (XRD) residual stress measurements point to a variety of loading conditions especially at raceway surfaces that are associated with several competing failure mechanisms. The corresponding lifetime reduction can range from the lower fatigue strength region to material ratcheting in extreme cases. Relevant position of the microstructural changes and nature of the failure mechanisms are characterized. The time alteration of the XRD material parameters measured at or near the surface and at the depth of the maximum equivalent stress correlates, in a different manner, with the statistical parameter of the 10 % bearing life. Both failure modes are illustrated by concrete examples. Contaminated lubricant and boundary lubrication, which represent practically important surface‐induced failures, are discussed in more detail. Gray staining, i.e. shallow pitting, often occurs without distinct indication of global material aging by means of XRD characteristics. Here, scanning electron microscopy observations and electron microprobe analyses point to corrosion fatigue as acting surface failure mechanism. The interaction between material and lubricant under complex loading regimes particularly of mixed friction and corrosion opens further failure research areas in the field of tribology.