Synthesis,properties, and solid-state assemblies of β-alkyl-substituted dipyrrolyldiketone BF2 complexes

In this paper, the synthesis and solid-state structures of β-alkyl-substituted dipyrrolyldiketone BF₂ complexes are discussed; these complexes can function as π-conjugated acyclic anion receptors (“molecular flippers”) and are potential building subunits of anion-responsive π-conjugated oligomers or polymers. Modes of the solid-state assemblies in these complexes determined by performing single-crystal X-ray analysis are found to depend on the lengths of the alkyl chains at the β-positions. A β-methyl-substituted receptor has a highly planar structure, which efficiently forms stacking assemblies in the core π-plane in the solid state, while a β-ethyl-substituted receptor shows no stacking assemblies due to the presence of bulky ethyl moieties, which form only dimeric structures by hydrogen bonding. β-Alkyl-substituted anion receptors can be used not only as monomer units of stimuli-responsive polymeric macromolecules but also as components of solid-state electronic materials.     

Rate Effects on the Stress-Strain Behaviour of Eps Geofoam

The rate-dependency of the stress-strain behavior of EPS (Expanded Polystyrene) geofoam with densities of 19.3 and 28.0 kg/m³ was investigated by performing unconventional unconfined compression tests. A set of monotonic loading (ML) tests were performed at different constant values of vertical (axial) strain rate, ε_v. The ε_v value was stepwise changed many times and several sustained loading (SL) tests were performed during otherwise ML at a constant ε_v in other tests. A number of SL tests were performed during global unload and reload cycles to infer the stress-strain relation when ε_v=0. The elastic properties were evaluated by applying minute unload/reload cycles during otherwise ML. The rate-dependent stress-strain behaviour observed in these tests was described by an elasto-viscoplastic model (i.e., a non-linear three-component model), for which the vertical (axial) stress, σ_v, consists of inviscid and viscous components, σ_v^f and σ_v^v, while ε_v consists of elastic and irreversible components, ε_v^e and ε_v^ir. It is shown that the viscous property of EPS geofoam is of Isotach type in that, under the loading conditions where ε_v^ir is always positive, the current σ_v^v value is a unique function of instantaneous ε_v^ir and ε_v^ir, therefore the strength increases with ε_v. This viscous property was quantified based on the test results and incorporated into the model. The rate-dependent stress-strain behaviour, including the creep behaviour, observed in the experiment is simulated very well by the proposed model. In particular, the fact that the creep strain becomes significant when the sustained σ_v value becomes larger than the inviscid yield vertical stress is well simulated.     

A Simple Pneumatic Loading System Controlling Stress and Strain Rates for One-Dimensional Compression of Clay

A simple but automated pneumatic loading system that can control the stress and strain rates for one-dimensional (1D) compression of clay was developed. The rate-dependency of stress-strain behaviour due to the viscous property of clay was investigated by 1D compression tests on standard-size specimens by various loading methods: 1) Standard Consolidation Tests (SCTs), stepwise increasing the axial stress two times every one day; 2) ordinary Constant-Rate-of-Strain (CRS) tests at different strain rates; 3) special CRS tests including unloading and reloading cycles with different stress amplitudes at strain rates of which the absolute value was either kept constant throughout respective tests or changed at the start of reloading; and 4) special CRS tests including a number of sustained loading (SL) during otherwise primary loading or unloading or reloading at constant strain rate. Sufficiently low strain rates were employed to ensure essentially fully drained condition. The followings were found. Despite that the newly developed pneumatic loading system is rather simple, 1D compression tests following such various loading histories as above can be performed on four types of clay rather accurately. The stress-strain behaviour of clay is significantly rate-dependent, exhibiting significant creep strains at SL stages. The creep strain rate is significantly different whether SL starts during otherwise primary loading or unloading or reloading, controlled by the magnitude and sign of the initial strain rate at the start of SL. The whole observed trends of rate-dependent stress-strain behaviour can be qualitatively explained by the non-linear three-component elasto-viscoplastic model extended to cyclic loading conditions.     

A pre-heating vaporization technology of coal-water-slurry for the gasification process

A pre-heating vaporization technology of coal water slurry, CWS, was developed to increase the efficiency of coal gasification with the reduction of oxygen consumption. A CWS pre-heating experimental unit having a capacity of 2.0 tons-coal/day was manufactured. After the CWS was heated to 573 K at about 10 MPa, water in CWS was continuously vaporized in a tube of which the diameter increased gradually (2–10 mm I.D.), and dry coal particles with steam were atomized and fed to a vessel. No aggregation of coal particles was observed in the atomized samples. The temperature and the pressure distributions of the fluid were calculated with empirical heat transfer and pressure drop correlations. The calculated results well corresponded to the experimental data measured in some test points. Using the calculation model, a large scale apparatus of 100 tons-coal/day was designed using KNO₃ + NaNO₂ + NaNO₃ molten salt as a heating medium.     

Multifunctional Initiator with Platinum-Acetylide Dendritic Core for Living Polymerization of Isocyanides

A novel multifunctional initiator has been developed by peripheral modification of a Pt-acetylide dendrimer. Pd–Pt μ-ethynediyl units were introduced to the first-generation dendrimer by a divergent method. The dendritic initiator was applicable to the living polymerization of aryl isocyanides, producing high molecular weight polymers with a narrow polydispersity index in quantitative yields. The ³¹P NMR spectrum of the resulting polymer suggested that all Pd–Pt μ-ethynediyl units in the dendritic molecule actually functioned as an initiator.     

TEM/STEM Observation of ZrC Coating Layer for Advanced High-Temperature Gas-Cooled Reactor Fuel, Part II

The Japan Atomic Energy Agency (JAEA) has started to study and develop zirconium carbide (ZrC)-coated fuel particles for advanced high-temperature gas-cooled reactors. The ZrC coating layer has been fabricated at JAEA by chemical vapor deposition using a pyrolytic reaction of zirconium bromide. The microstructures of the ZrC layers, whose nominal deposition temperatures could be measured and controlled during the deposition process, were characterized by means of TEM and STEM. In the present study, three batches were prepared and compared with each other as well as the previous batches. The crystallographic orientation of ZrC with regard to the growth direction in the ZrC layers deposited at a constant temperature of 1630 K was different from that deposited at varying temperatures in the 1493–1823 K range. A thin layer of turbostratic carbon was observed at the boundary between pyrolytic carbon and ZrC in particles deposited at the highest temperature among those used in this study (the nominal temperature was 1769 K); no such structure was found in a batch deposited at a lower temperature (the nominal temperature was 1632 K). Therefore, precise control of temperature is shown to be critical to the formation of good ZrC coatings.     

Size-dependent separation of graphene oxide by deformation of packed-gel in a chromatographic column

ABSTRACT

A deformable gel-packed chromatographic column was used to separate as-synthesized graphite oxide with different sizes. The synthesized gel (56 µm) was deformed by pressure of the fluid flow and the gaps in the gels showed a range of sizes. A suspension of graphene oxide (0.1 g/L, 10 mL) was injected, and graphene oxide in the elution had a size at 0.56 μm and 0.14 μm, whereas in half upper and bottom domain of the gel layer graphene oxide had a size at 33 µm and 2.9 µm, respectively, demonstrating that graphene oxide suspension was separated by size through gel layer.