Phase transition in swollen gels

Summary The photoelastic behaviour of two networks — polyacrylamide (PAAm) and of a network prepared by the copolymerization of acrylamide with 5 mol.% sodium methacrylate — was investigated in water-acetone mixtures. For the PAAm network the dependence of all photoelastic characteristics on the composition of the mixture is continuous. At 54 vol.% acetone in the mixture, the ionized network undergoes a transition which gives rise to jumpwise changes in the shear modulus, deformational-optical coefficient, C, and in the refractive index of the gel, n_g. While in the collapsed state the optical anisotropy of the statistical segment is negative, –3×10^–24 cm³ (indicating an interaction between the side chains), in the expanded state it is positive, 0.5 × 10^–24 cm³. The dependence of all optical characteristics on the composition of the mixtures suggests that: (a) in both networks we have a transition between two conformational states of the chain; while for the ionized network the transition is a discrete one, for the nonionized network it takes place in the range between 30 and 45 vol.% acetone in the mixture; (b) in both networks the gels are optically homogeneous throughout the whole range of compositions of the mixtures (and thus also in the close vicinity of the collapse of the ionized network).     

Neues Verfahren zur Methanol- und Ammoniak-Synthese. Der Gas/Feststoff/Feststoff-Rieselströmungsreaktor – ein neuer Reaktortyp zur Führung chemischer Gleichgewichtsprozesse

New process for the production of methanol and ammonia. The gas/solids/solids thrickle flow reactor – a new kind of reactor for chemical equilibrium processes . A new process for the production of ammonia or methanol has been developed in the high pressure laboratory of Twente Technical University. The reactants can be made to react completely in a single reactor pass, thus avoiding expensive recirculation. Complete reaction without recirculation is accomplished by a combination of two reversible processes: a chemical reaction and a selective adsorption of the reaction product on a solid in constant flow. On introduction of an inert-gas free stoichiometric mixture of reactants into the reactor, the exhaust gas outlet can be closed. If there is an excess of one of the reactants or of inert gas, it can leave from the top of the reactor. Such a process has been accomplished in a new gas/solids/solids trickle flow reactor in which a granulated adsorbent ?rains”? through a fixed bed of catalyst. The present article describes the use of this kind of reactor for methanol synthesis. Considerable savings in production costs are expected relative to the modern Lurgi low pressure process. A pilot plant is to be built to characterize and evaluate the new process. Royal Dutch Shell has registered a patent application.     

Diffusion-related implications for langasite resonator operation

Oxygen and gallium diffusivities in langasite were experimentally determined by analysis of diffusion profiles of 18O and 71Ga tracers by SIMS analysis as functions of temperature and doping. Strontium-enhanced diffusivities and activation energies of approximately 1.2+/-0.2 eV confirm the predominant role of oxygen vacancies in controlling the electrical conductivity of langasite at elevated temperature and oxygen partial pressure. The potential impact of high levels of porosity and the use of an oxygen primary ion beam on the accuracy of some of the data is discussed. The gallium diffusivity, with activation energy of 3.13 eV, was found to be more than two orders of magnitude lower than that of oxygen. Surface exchange measurements enabled estimation of gallium loss at elevated temperatures and oxygen partial pressure; the level is not believed to be of major concern for resonator performance.     

Friction Sensitivity of Nitramines. Part Ⅱ: Comparison with Thermal Reactivity（英）

The friction sensitivity (FS) of five linear and eight cyclic nitramines has been determined.Arrhenius parameters of non-autocatalyzed thermal decomposition of these nitramines were used for comparison...     

Use of Polyaminocarboxylic Acids as Hydrophilic Masking Agents for Fission Products in Actinide Partitioning Processes

During the partitioning of trivalent actinides from High Active Raffinate (HAR) solutions, most processes have to cope with an undesirable co-extraction of some of the fission products. Four hydrophilic complexing agents of the group of polyaminocarboxylic acids, namely EDTA, HEDTA, DTPA, and CTDA were tested and compared for their ability to complex fission products in a simulated PUREX raffinate solution, thereby preventing their extraction into an organic solvent. Several solvents, based on TODGA and the DIAMEX reference molecule DMDOHEMA, that are commonly known to show quite high Zr and Pd co-extraction, were studied. Our investigations ultimately resulted in a substitution of oxalic acid and HEDTA by cyclohexanediaminetetraacetic acid (CDTA). A small addition of this hydrophilic complexing agent to the feed decreased the distribution ratios of Zr from 100 to <0.01. The suppression of Pd was also very effective, resulting in >90% of the metal retained in the feed solution. The extraction of trivalent actinides and lanthanides was not negatively affected by the presence of CDTA. Furthermore, experiments with high concentrations of Zr proved the applicability of this new masking agent. The suppression of Zr and Pd extraction was also verified at a high Pu loading which makes CDTA as a masking agent attractive for grouped actinide extraction processes (GANEX) as well as DIAMEX-SANEX type separations.     

Analysis of multiple cracks in thin coating on orthotropic substrate under mechanical and residual stresses

The analysis addresses a typical failure development pattern in thin films consisting of a system of multiple surface cracks leading to and branching along or near the interface between the film and the base material. The process is driven by thermal residual stresses and/or mechanical loading. Due to the high temperature gradients during the fabrication process, usually a net of surface cracks develops, which gives the appearance of a granular structure of the surface. A periodic array of parallel surface cracks is assumed. A “unit cell” or single cracked segment attached to the substrate is analyzed instead by assuming the channel cracks are spaced more or less uniformly and perfectly aligned in parallel in the transverse direction of the coating. The analysis is specialized to orthotropic and transversally isotropic materials. The problem is solved using FEM combined with the reciprocal theorem. Matched asymptotic procedure [Leguillon D, Sanchez-Palencia E. Computation of singular solutions in elliptic problems and elasticity. Paris: Masson; 1987; Vu-Quoc L, Tran VX. Singularity analysis and fracture energy-release rate for composites: piecewise homogenous-anisotropic materials. Comput Methods Appl Mech Engng 2006;195:5162-97] is used to derive the change of potential energy. Higher-order terms in the asymptotics are considered. The competition between penetration and debond for periodically distributed edge cracks especially near the critical value of the ratio of fracture spacing to the layer thickness is examined.