Short time spreading and wetting of offset printing liquids on model calcium carbonate coating structures

Spreading of oils and water on porous and pre-saturated model carbonate coating structures was studied with high speed video imaging. The short-time data were complemented with long time absorption and wicking experiments. The results indicate a strong dependence between surface structural features of the pigment tablets and water spreading at short times, both in non-saturated and water pre-saturated cases, while the oil spreading is mainly dependent on the liquid properties. Sodium polyacrylate dispersant on pigment surfaces is shown to contribute to water spreading and absorption. On pre-saturated structures the liquid-liquid interactions are dominant and the majority of results support spreading according to the molecular kinetic model. The evidence supports the hypothesis of S. Rousu, P. Gane, and D. Eklund, ["Influence of coating pigment chemistry and morphology on the chromatographic separation of offset ink constituents," in The Science of Papermaking Transactions of the 12th Fundamental Research Symposium, FRC The Pulp & Paper Fundamental Research Society, Oxford, UK, 2001, p. 1115] that at long times the oils absorb into the porous structure at a rate proportional to the ratio of viscosity and surface tension, provided there is no sorptive action with the binder. A combination of nanosized pores and large surface area is useful for providing sufficient absorption capability for carbonate based coatings.     

Effects of fibre-surface morphology on the mechanical properties of Porifera-inspired rubber-matrix composites

In this paper, mineralised organic fibre morphologies, inspired by the structures of Porifera (sponges) are correlated to the mechanical performance of fibre reinforced rubbers. The mineralised structures are rich in calcium carbonate and silica. These compounds nucleate and precipitate on the fibre surfaces yielding different morphologies as a function of mineral ion concentrations. Smaller mineralised precipitates manifestly improve the mechanical performance of composites while thicker precipitates enveloping the fibres give rise to inferior properties. Mechanisms and evidenced reasoning for these differences are reported herein.     

Time-dependent density-functional theory in the projector augmented-wave method

We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we found perfect agreement in the calculated photoabsorption spectra. We discuss the strengths and weaknesses of the two methods as well as their convergence properties. We demonstrate different applications of the methods by calculating excitation energies and excited state Born-Oppenheimer potential surfaces for a set of atoms and molecules with the linear-response method and by calculating nonlinear emission spectra using the time-propagation method.     

Reaction of Selenium with Bromine in the Presence of Methyltriphenylphosphonium Bromide: Syntheses and Crystal Structures of [PMePh3]2[Se2Br6] and [PMePh3]2[SeBr6(SeBr2)2]

The brown crystals of [PMePh₃]₂[Se₂Br₆] ( 1 ) and red crystals of [PMePh₃]₂[SeBr₆(SeBr₂)₂] ( 2 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of methyltriphenylphosphonium bromide. The crystal structures of 1 and 2 has been determined by the X‐ray methods and refined to R = 0.0373 for 2397 reflections and 0.0397 for 3417 reflections, respectively. The salt 1 crystallizes in the monoclinic space group P2₁/n with the cell dimensions a = 13.202(5) Å, b = 11.954(4) Å, c = 13.418(6) Å, β = 93.08(4)° (193(2)). The crystals of 2 are triclinic, space group with the cell dimensions a = 10.266(3) Å, b = 11.311(3) Å, c = 11.619(2) Å, α = 108.87(2)°, β = 105.72(2)°, γ = 99.40(2)° (193(2) K). In the solid state structure of 1 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square planar SeBr₄ units sharing a common edge through two μ‐bridging Br atoms. The terminal Se^II–Br bonds are 2.3984(11) and 2.4273(11) Å, whereas the bridging μBr–Se^II bonds are 2.7817(11) and 2.9081(12) Å. In the solid state the trinuclear [SeBr₆(SeBr₂)₂]^2? anion of 2 is centrosymmetric too and contains a nearly regular [SeBr₆] octahedron where the four equatorial bromo ligands each have developed bonds to the Se^II atoms of the SeBr₂ molecules. The contacts between the bridging bromo and the Se^II atoms of the SeBr₂ molecules are 3.0603(15) and 3.1043(12) Å, and can be interpreted as bonds of the donor‐acceptor type with the bridging bromo ligands as donors and the SeBr₂ molecules as acceptors. The Se^IV–Br distances are in the range 2.5570(9)–2.5773(11) Å and the Se^II–Br bond lengths in coordinated SeBr₂ molecules – 2.3411(12) and 2.3421(10) Å.     

Acid-catalyzed hydrolyses of bridged bi- and tricyclic compounds-XII: Kinetics of hydration of 2-norbornenone,a special β,γ-unsaturated ketone

The reaction rates, activation parameters, solvent deuterium isotope effects, and dependences of rates on acid concentration measured for the hydration of 2-norbornenone and its four Me-substituted homologs in aqueous acid agree with the slow protonation of the CC double bond (A-S_E2 mechanism). Thus the mechanism differs from that reported for the isomerization (to α,β-unsaturated ketones) of unbridged β,γ-unsaturated ketones, e.g. 3-cycloalkenones and Δ⁵-3-ketosteroids, under catalysis by acid.     

A problem on heat conduction in an insulated wire solved by numerical inverse Laplace transform

A problem of transient heat conduction in an insulated wire is solved by use of Laplace transform and numerical inversion. The problem is solved for the radiation boundary condition and also for the boundary condition of no heat flux through the outer surface of the insulation. The results are presented both numerically with four significant figures and graphically. Asymptotic expansions are derived for small and large values of the time variable. The numerical inversion of the Laplace transform is checked by comparison with the asymptotic expansions and with the numerical results obtained by a numerical inversion formula utilizing one more abscissa than the previous one.     

Release of K,Cl, and S during combustion and co-combustion with wood of high-chlorine biomass in bench and pilot scale fuel beds

Studies of the release of critical ash-forming elements from combustion of biomass are typically conducted with small sample masses under well controlled conditions. In biomass combustion on a grate, secondary recapture and release reactions in the fuel-bed may affect the overall release and partitioning of these elements. Earlier work by the authors on the release of K, Cl, and S from a high-chlorine biomass (corn stover) in a lab-scale setup is, in the present work, supplemented with novel results from a bench-scale fixed bed reactor and a 100 kW moving grate pilot facility. The results from the bench-scale reactor indicate that S and K release are not significantly affected by secondary reactions, while Cl is partly recaptured by secondary reactions in the char. A linear increase in K-release was observed from 50% at 906 °C to almost 80 wt.% at 1234 °C when firing only corn stover. A similar release profile was observed for Cl, from 65% to nearly 100%. Complete release of S was achieved at 1234 °C with a linear increase from 70% at 906 °C. Co-combustion of corn stover with low-Cl wood chips served to increase the bed temperature, resulting in complete and close to complete release of Cl and S, respectively. An increase in the relative K-release was observed when increasing the wood chip fraction from 40% to 100% (energy basis). Pilot scale flue gas results indicate that the share of Cl released as HCl decreases towards 0% as the share of wood chips is increased towards 100%. Hence, co-combustion of corn stover with wood chips is expected to decrease the absolute release of KCl due to the lower feedstock quantity of Cl, however, increase the relative release of Cl as KCl.