Expected and unexpected plastic behavior at the micron scale: An in situ μLaue tensile study

The study of mechanical properties in micron- and submicron-sized metal crystals raises fundamental questions about the influence of size on different aspects of plasticity. In situ characterization of the microstructure evolution during loading is necessary to understand the physics underlying crystal deformation. In situ μLaue diffraction is able to provide unique statistical information on the evolution of type and density of stored dislocations. Here we show macroscopically expected and unexpected plastic behavior at low strains, observed during in situ μLaue tensile tests on micron-sized, single slip oriented Cu samples. Regardless of the initial behavior, a steady state is reached which qualifies a technical yield criterion at the micron scale.     

Optimizing the ring-rolling operation with process control

To minimize costs in the manufacture of ring-shaped products, the ring-rolling process must be controlled efficiently. Toward this end, a recently developed control system allows nearly unattended operation of ring-rolling machines. The control system determines optimum preform geometry, thereby minimizing scrap; it also continuously monitors the process to adjust for deviations from set conditions. Various operations can be controlled, and process efficiency and quality are greatly improved.     

Spatially resolved nanoscale chemical and mechanical characterization of ZDDP antiwear films on aluminum–silicon alloys under cylinder/bore wear conditions

summary  Understanding the lubrication of aluminum–silicon (Al–Si) alloys (>18 Si) under conditions similar to those in the cylinder/bore system is vital to determining their applicability to current engine designs. A novel investigation of the location of zinc-dialkyl-dithiophosphate (ZDDPs) antiwear (AW) film formation on an Al–Si alloy has been performed using X-ray absorption near edge structure (XANES) analysis, X-ray photoelectron emission spectroscopy (X-PEEM), and imaging nanoindentation techniques. A study of the initial stages of wear (10 min) to prolonged rubbing (60 min) was performed. The findings show that the film forms primarily on the raised silicon grains and is consistent with a zinc polyphosphate glass. The film has an elastic modulus of ~70 GPa and a similar elastic response to a ZDDP AW film formed on steel under the same conditions. This provides the first direct observation and characterization of a ZDDP antiwear film on Al–Si alloys using spatially resolved chemical and mechanical techniques at the nanoscale.     

Metallurgy and processing of coloured gold intermetallics — Part I: Properties and surface processing

Blue and purple gold alloys form in the alloying systems of gold with gallium/indium and aluminium respectively and are known to be very brittle and to possess low corrosion resistance. Taking into account these drawbacks this paper describes the results of a European funded research project. The properties of the blue and purple gold alloys and coatings such as corrosion resistance, metal release rates, hardness and colour and the influence of alloying additions on these properties are presented and discussed. Surface engineering techniques and investment casting were used for manufacturing of jewellery items with selectively coated coloured surface. Coatings of AuGa₂ and AuIn₂ blue gold alloys were applied on 18kt gold and Sterling silver jewellery by electroplating, laser/torch cladding or dipping into liquid gallium. The suitability of blue gold coatings for jewellery purposes will be discussed in the light of reliability and feasibility. The work consists of two parts. Part I describes properties and surface processing techniques while Part II deals with investment casting and related alloy design of coloured gold alloys.     

Correlations for the particle deposition rate accounting for lift forces and hydrodynamic mobility reduction

A numerical procedure is presented which allows one to predict the deposition rate of microparticles suspended in a liquid flow onto the confining walls. Particle transport is not only diffusive but also affected by hydrodynamically induced lift force and reduced particle mobility. An appropriate expression for the lift‐induced migration is introduced into the numerical procedure. Its results agree quanititatively with previously published experimental data showing a significant effect of lift‐induced particle transport. Based on the numerical results algebraic correlations are obtained, which enable to calculate the particle deposition rate in situations where lift forces and mobility reduction diminishes the particle deposition rate.     

Characterization of New PPARγ Agonists: Analysis of Telmisartan’s Structural Components

Telmisartan was originally designed as an AT₁ antagonist but was later also characterized as a selective PPARγ modulator. This study focused on the identification of the essential structural motifs of telmisartan for PPARγ activation activity, elucidating the individual SAR of each different component (shown).

     

Characterization of New PPARγ Agonists: Benzimidazole Derivatives – the Importance of Position 2

Probing SAR : The 1‐(biphenyl‐4‐ylmethyl)‐1H‐benzo[d]imidazole moiety is known to be an essential structural component of telmisartan for PPARγ activation. This study focused on the substituents at position 2 of the benzimidazole in an attempt to optimize PPARγ activation. In particular, the elongation of the alkyl chain and the introduction of an aromatic ring system were studied (shown).

     

Understanding selective oxidations

Functionalizing organic molecules is an important value-creating step throughout the entire chemical value-chain. Oxyfunctionalization of e.g. C-H or C=C bonds is one of the most important functionalization technologies used industrially. The major challenge in this field is the prevention of side reactions and/or the consecutive over-oxidation of the desired products. Despite its importance, a fundamental understanding of the intrinsic chemistry, and the subsequent design of a tailored engineering environment, is often missing. Industrial oxidation processes are indeed to a large extent based on empirical know-how. In this mini-review, we summarize some of our previous work to help to bridge this knowledge gap and elaborate on our ongoing research.     

Biphasic and Flow Systems Involving Water or Supercritical Fluids

Two processes are described for improving reaction rates for relatively hydrophobic substrates in aqueous biphasic systems. In the first, 1-octyl-3-methylimidazolium bromide ([Octmim]Br) increases the rate of hydroformylation of 1-octene from 8% conversion in 24 h to full conversion of 1.5 h. Phase separation is fast and catalyst retention is good. 1-Hexyl-3-methylimidazolium bromide gives little rate enhancement, whilst 1-decyl-3-methylimidazolium bromide gives stable emulsions., The mechanism of action of these additives is discussed. In the second approach, functionalising PPh₃ with amidine groups allows the rhodium catalysed hydroformylation of 1-octene in toluene with a very high reaction rate. The catalyst can be switched between toluene and water by bubbling CO₂ and back into toluene by bubbling N₂ at 60 °C. This switching has been used to separate the catalyst from hydrophobic (from 1-octene) or hydrophilic (from allyl alcohol) aldehydes obtained from hydroformylation reactions. CO₂ expanded liquids have been shown to be effective media for transporting substrates and catalysts over supported ionic liquid phase (SILP) catalysts. The advantages offered over all gas phase and liquid phase catalysts are discussed.     

Probing enzyme promiscuity of SGNH hydrolases

Several hydrolases of the SGNH superfamily, including the lipase SrLip from Streptomyces rimosus (Q93MW7), the acyl-CoA thioesterase I TesA from Pseudomonas aeruginosa (Q9HZY8) and the two lipolytic enzymes EstA (from P. aeruginosa, O33407) and EstP (from Pseudomonas putida, Q88QS0), were examined for promiscuity. These enzymes were tested against four chemically different classes of a total of 34 substrates known to be hydrolysed by esterases, thioesterases, lipases, phospholipases, Tweenases and proteases. Furthermore, they were also analysed with respect to their amino acid sequences and structural homology, and their phylogenetic relationship was determined. The Pseudomonas esterases EstA and EstP each have an N-terminal domain with catalytic activity together with a C-terminal autotransporter domain, and so the hybrid enzymes EstA(N)-EstP(C) and EstP(N)-EstA(C) were constructed by swapping the corresponding N- and C-terminal domains, and their hydrolytic activities were compared. Interestingly, substrate specificity and kinetic measurements indicated a significant influence of the autotransporter domains on the catalytic activities of these enzymes in solution. TesA, EstA and EstP were shown to function as esterases with different affinities and catalytic efficacies towards p-nitrophenyl butyrate. Of all the enzymes tested, only SrLip revealed lipase, phospholipase, esterase, thioesterase and Tweenase activities.