Simultaneous optimization of thermochemical data for liquid iron alloys containing C,N, Ti,Si, Mn,S, and P

A data base of thermochemical parameters for liquid iron-base alloys containing C, N, Ti, Si, Mn, S, and P is presented. A matrix of linear inequalities describing the experimental data among these elements was constructed. A set of internally consistent thermochemical data permitted by the uncertainties of the experiments was evaluated by means of a linear programming algorithm. Expressions for the interaction parameters of the solutes and the Gibbs energies of formation of the carbides, nitrides, carbonitrides, and sulfides of titanium were simultaneously optimized. It is shown that the resulting thermochemical data base reproduces the experimental data satisfactorily. DOMINIQUE BOUCHARD, formerly Graduate Student, école Polytechnique de Montréal.     

Analyzing proposals for improving authentication on the TLS-/SSL-protected Web

“Secure” Web browsing with HTTPS uses TLS/SSL and X.509 certificates to provide authenticated, confidential communication between Web clients and Web servers. The authentication component of the system has a variety of weaknesses, which have led to a variety of proposals for improving the current environment. In this paper, we survey, analyze, compare and contrast five prominent proposals. To do this, we attempt to systematically capture the properties one might require of such a system: authentication properties, forensics/privacy properties, usability properties and pragmatic properties. Enumerating these properties is an important part of understanding these proposals and the nature of the authentication problem for the secure Web. Finally, we offer a few conclusions and suggestions pertaining to these proposals and possible future directions of research.     

Surfactant-free emulsion polymerisation of methyl methacrylate and methyl acrylate using intensified processing methods

The feasibility of enhancing the latex yield and colloid characteristics in the surfactant-free emulsion polymerisation (SFEP) of methyl methacrylate (MMA) and methyl acrylate (MA) through the use of intensified processing technologies is reported in this paper. The effects of high power ultrasonic energy as a well-established technique for mixing and mass transfer enhancements were compared with thermal initiation in a conventional mechanically agitated reactor. Although increases in ultrasonic power input resulted in higher rates of reaction and larger particles in the MMA polymerisation, reaction yields were nevertheless found to be low compared with the thermally initiated stirred tank reactor experiments. This was attributed to the low frequency ultrasound used (24 kHz) that was observed to provide excellent emulsification but was ineffective in terms of radical generation. The results for a thermally initiated SFEP of MA in a narrow channel reactor as an example of a continuous flow reactor technology showed that reaction rates were comparable with those achieved in the stirred tank reactor but at only a fraction of the specific power input whilst smaller particles with a tighter distribution are generated. These effects highlight the process intensification characteristics of the narrow channel reactor for the SFEP of MA.     

Readily Accessible Oxazolidine Nitroxyl Radicals: Bifunctional Cocatalysts for Simplified Copper Based Aerobic Oxidation

Using a two‐step procedure a range of bifunctional oxazolidine nitroxyl radicals have been prepared. The application of these co‐catalysts to the copper‐based aerobic oxidation of alcohols was then investigated. From these studies it was found that the parent tetramethyloxazolidine nitroxyl radical L1 was competent for oxidation in the presence of 2,2′‐bipyridine, and the bifunctional pyridyl‐containing nitroxyl radicals L2 and L3 could be used in the absence of additional coordinating ligands. Following optimization, the scope of this simplified transformation was explored, demonstrating that a range of primary and secondary benzylic alcohols are readily oxidized. In addition, the oxidation of allylic alcohols and hydroquinone can be achieved.     

Effect of sparse long‐chain branching on the step‐strain behavior of a series of well‐defined polyethylenes

The effect of sparse long chain branching, LCB, on the shear step‐strain relaxation modulus is analyzed using a series of eight high‐density polyethylene (HDPE) resins. Strains of 1 to 1250% are imposed on materials with LCB content ranging from zero to 3.33 LCB per 10,000 carbon atoms. All materials are observed to obey time–strain separation beyond some characteristic time, τ_k. The presence of LCB is observed to increase the value of τ_k relative to the linear resin. The behavior of the relaxation modulus at times shorter than τ_k is investigated by an analysis of the enhancement seen in the linear relaxation modulus, G⁰(t), as a function of strain and LCB content. This enhancement is seen to (1) increase with increasing strain in all resins, (2) be significantly larger in the sparsely branched HDPE resins relative to the linear HDPE resin, and (3) increase in magnitude with increasing LCB content. The shape and smoothness of the damping function is also investigated. The finite rise time to impose the desired strain is compared to the Rouse relaxation time of linear HDPE resins studied. Sparse LCB is found to increase the magnitude of the relaxation modulus at short times relative to the linear resin. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Effect of solvent evaporation rate on the crystalline state of electrospun Nylon 6

The role of solvent evaporation on the crystalline state of electrospun Nylon 6 fibers was examined by electrospinning into a closed chamber filled with different concentrations of solvent vapor. It was found that the thermodynamically stable α form became increasingly dominant in Nylon 6 fibers electrospun out of both 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and formic acid as the vapor phase solvent concentration increased. It is believed that the formation of the metastable γ form is due in part to the fast solvent evaporation kinetics associated with the electrospinning process. By varying the vapor phase concentration and thus the rate of solvent evaporation during electrospinning, we were able to vary the resulting crystal structure of the electrospun Nylon 6, as shown by XRD, Raman and FTIR.     

Biocatalysis with Thermostable Enzymes: Structure and Properties of a Thermophilic ‘ene’‐Reductase related to Old Yellow Enzyme

We report the crystal structure of a thermophilic “ene” reductase (TOYE) isolated from Thermoanaerobacter pseudethanolicus E39. The crystal structure reveals a tetrameric enzyme and an active site that is relatively large compared to most other structurally determined and related Old Yellow Enzymes. The enzyme adopts higher order oligomeric states (octamers and dodecamers) in solution, as revealed by sedimentation velocity and multiangle laser light scattering. Bead modelling indicates that the solution structure is consistent with the basic tetrameric structure observed in crystallographic studies and electron microscopy. TOYE is stable at high temperatures (T_m>70 °C) and shows increased resistance to denaturation in water‐miscible organic solvents compared to the mesophilic Old Yellow Enzyme family member, pentaerythritol tetranitrate reductase. TOYE has typical ene‐reductase properties of the Old Yellow Enzyme family. There is currently major interest in using Old Yellow Enzyme family members in the preparative biocatalysis of a number of activated alkenes. The increased stability of TOYE in organic solvents is advantageous for biotransformations in which water‐miscible organic solvents and biphasic reaction conditions are required to both deliver novel substrates and minimize product racemisation.