On the eddy diffusivities for momentum and heat

Summary From a simple consideration, the eddy diffusivities for momentum and heat are shown to be equal in terms of statistical properties of turbulence. A universal semi-empirical expression for the eddy diffusivities in a turbulent shear flow is obtained in terms of the distance from the solid boundary and flow properties.     

Synthesis,Characterization and Photoluminescence of Lanthanide Metal‐organic Frameworks,Constructed from Triangular 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate Ligands

Eight isomorphous metal‐organic frameworks: [Ln₂(TATAB)₂(H₂O)(DMA)₆]·5H₂O (Ln = Sm ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Dy ( 5 ), Er ( 6 ), Tm ( 7 ), Yb ( 8 )); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H₂O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature.     

Profile monitoring of reflow process using approximations of mixture second‐order polynomials

Lately, profile monitoring has received considerable attention in the statistical process control research field. This paper proposes a novel monitoring framework for the reflow process data, which uses two goodness‐of‐fit criteria to select the change points in the mixture polynomial model. Among change points, the mixture second‐order polynomials are utilized to piecewisely approximate the nonlinear profile data of the reflow process. The well‐known Hotelling T² and proposed EWMA₄ control charts are then employed to monitor the parameter estimates. The experimental results demonstrate that the proposed monitoring framework presents better performances in detecting outlying profiles than the conventional methods in phase I. In phase II, the performance of the proposed framework is assessed in terms of the out‐of‐control average run length. Copyright © 2014 John Wiley & Sons, Ltd.     

The Effect of Controlled Dopant Concentration on the Performance of Blue Polymer Light‐emitting Diodes

The performance of a blue polymer light‐emitting diodes (PLED) was significantly improved by doping a controlled amount (<1%) of a hole transport molecule N,N′‐bis‐(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4″‐diamine (NPB) into the emitting layer. Hole carrier mobility of the blue emitting polymer, BP105 (trade name of The Dow Chemicals Co.), increased from 5.27 × 10^‐7 cm^‐2/Vs of the pristine BP105 to 1.80 × 10^‐6 cm^‐2/Vs with the addition of 1% NPB in BP105. The enhanced carrier mobility greatly promoted performance of a blue PLED device with a device structure of ITO/PEDOT:PSS/BP105+x% NPB/LiF/Ca/Al. Luminance increased from 573 cd/m² to 2,720 cd/m² at 6V and efficiency increased from 1.1 lm/W to 1.6 lm/W at 1,000 cd/m² with 1% NPB in BP105. The most important improvement was an increase in the lifetime of the blue device from 80 to 120 hours at an initial luminance of 400 cd/m². We found that by choosing the appropriate dopant with good energy alignment and controlled dopant concentration, the performance of a blue PLED device could be greatly improved.     

Quantifying temperature and flow rate effects on the performance of a fixed-bed chromatographic reactor

Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria.     

New Insights into Keggin‐Type 12‐Tungstophosphoric Acid from 31P MAS NMR Analysis of Absorbed Trimethylphosphine Oxide and DFT Calculations

The acid and transport properties of the anhydrous Keggin‐type 12‐tungstophosphoric acid (H₃PW₁₂O₄₀; HPW) have been studied by solid‐state ³¹P magic‐angle spinning NMR of absorbed trimethylphosphine oxide (TMPO) in conjunction with DFT calculations. Accordingly, ³¹P NMR resonances arising from various protonated complexes, such as TMPOH⁺ and (TMPO)₂H⁺ adducts, could be unambiguously identified. It was found that thermal pretreatment of the sample at elevated temperatures (≥423 K) is a prerequisite for ensuring complete penetration of the TMPO guest probe molecule into HPW particles. Transport of the TMPO absorbate into the matrix of the HPW adsorbent was found to invoke a desorption/absorption process associated with the (TMPO)₂H⁺ adducts. Consequently, three types of protonic acid sites with distinct superacid strengths, which correspond to ³¹P chemical shifts of 92.1, 89.4, and 87.7 ppm, were observed for HPW samples loaded with less than three molecules of TMPO per Keggin unit. Together with detailed DFT calculations, these results support the scenario that the TMPOH⁺ complexes are associated with protons located at three different terminal oxygen (O_d) sites of the PW₁₂O₄₀³⁻ polyanions. Upon increasing the TMPO loading to >3.0 molecules per Keggin unit, abrupt decreases in acid strength and the corresponding structural variations were attributed to the change in secondary structure of the pseudoliquid phase of HPW in the presence of excessive guest absorbate.     

Reactions of Ruthenium–Allenylidene Complexes Tethering a Cyclopropyl Group

Two cyclopropyl allenylidene complexes [Ru]=CCC(R)(C₃H₅) ([Ru]=[RuCp(PPh₃)₂], Cp=Cyclopentadienyl; R=thiophene ( 2a ) and R=Ph ( 2b )) are prepared from the reactions of [Ru]Cl with the corresponding 1‐cyclopropyl‐2‐propyn‐1‐ol in the presence of KPF₆. Thermal treatment, halide‐anion addition, and palladium‐catalyzed reactions of 2a and 2b all lead to a ring expansion of the cyclopropyl group, giving the vinylidene complexes 4a and 4b , respectively, each with a five‐membered ring. This ring expansion proceeds by C C bond formation between Cβ of the cumulative double bond and a methylene group of the cyclopropyl ring. In the reaction of 2a with pyrrole, consecutive formation of two C C bonds, one between C‐2 of pyrrole and Cγ of 2a and the other between C‐3 of pyrrole and Cα, results in the formation of 6a . The reaction proceeds by addition of pyrrole and 1,3‐proton shifts. The hydrogenation of 2a by NaBH₄ is carried out in different solvents. The cumulative double bonds are reduced regioselectively to give a mixture of 7a and 8a . Interestingly, use of different solvents leads to different ratios of 7a and 8a . Presence of a protic solvent like methanol in dichloromethane or chloroform solution increases the yield of 8a , thus revealing that both the rates of hydroboration and deboronation increase. The structures of two new complexes 4a and 6a have been firmly established by X‐ray diffraction analysis.     

A hybrid descent method for solving a convex constrained optimization problem with applications

The purpose of this paper is to introduce a hybrid descent algorithm for finding a common point in fixed‐point sets of quasi‐nonexpansive mappings and solution sets of variational inequality problems. In the framework of Hilbert spaces, the strong convergence of the hybrid descent algorithm is established. Numerical experiments for the bandwidth allocation, which demonstrate the effectiveness, performance, and convergence of the proposed algorithm, are provided.     

On a multistage discrete stochastic optimization problem with stochastic constraints and nested sampling

Mathematical Programming -