MOF-derived bimetallic NiCo nanoalloys for the hydrogenation of biomass-derived levulinic acid to γ-valerolactone

The selective hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) is one of pivotal reactions in many of the biorefinery schemes for the production of value-added chemicals and biofuels. Herein, we have fabricated carbon-supported bimetallic NiCo catalysts based on the metal–organic framework (MOF) material via a pyrolysis method. The as-obtained Ni₁Co₁ bimetallic catalyst outperforms monometallic counterparts in the catalytic performance of LA-to-GVL, with a nearly full conversion of LA and a GVL yield of 95.2%, in particular with an excellent catalyst stability up to seven consecutive runs at 160°C and 4 MPa H₂. Based on a combined characterization study by employing advanced techniques, for example, extended x-ray absorption fine structure (EXAFS), high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), and electron paramagnetic resonance (EPR), we reveal that the enhanced catalytic performance, in particular the excellent stability, could be attributed to the formation of the bimetallic alloys, which efficiently alleviates the metal leaching and sintering during catalysis.     

A robust learning based evolutionary approach for thermal-economic optimization of compact heat exchangers

This paper presents a robust, efficient and parameter-setting-free evolutionary approach for the optimal design of compact heat exchangers. A learning automata based particle swarm optimization (LAPSO) is developed for optimization task. Seven design parameters, including discreet and continuous ones, are considered as optimization variables. To make the constraint handling straightforward, a self-adaptive penalty function method is employed. The efficiency and the accuracy of the proposed method are demonstrated through two illustrative examples that include three objectives, namely minimum total annual cost, minimum weight and minimum number of entropy generation units. Numerical results indicate that the presented approach generates the optimum configuration with higher accuracy and a higher success rate when compared with genetic algorithms (GAs) and particle swarm optimization (PSO).     

Simultaneously achievement of high recoverable energy density and efficiency in sodium niobate-based ceramics

Journal of Materials Science: Materials in Electronics - Single lead-free Na0.73Bi0.09(Nb1???xTax)O3 (x?=?0, 0.10, 0.20, 0.30, and 0.40) ceramic phases were processed...     

Heifers with positive genetic merit for fertility traits reach puberty earlier and have a greater pregnancy rate than heifers with negative genetic merit for fertility traits

This study investigated the hypothesis that dairy heifers divergent in genetic merit for fertility traits differ in the age of puberty and reproductive performance. New Zealand's fertility breeding value (FertBV) is the proportion of a sire's daughters expected to calve in the first 42 d of the seasonal calving period. We used the New Zealand national dairy database to identify and select Holstein-Friesian dams with either positive (POS, +5 FertBV, n = 1,334) or negative FertBV (NEG, ?5% FertBV, n = 1,662) for insemination with semen from POS or NEG FertBV sires, respectively. The resulting POS and NEG heifers were predicted to have a difference in average FertBV of 10 percentage points. We enrolled 640 heifer calves (POS, n = 324; NEG, n = 316) at 9 d ± 5.4 d (± standard deviation; SD) for the POS calves and 8 d ± 4.4 d old for the NEG calves. Of these, 275 POS and 248 NEG heifers were DNA parent verified and retained for further study. The average FertBV was +5.0% (SD = 0.74) and ?5.1% (SD = 1.36) for POS and NEG groups, respectively. Heifers were reared at 2 successive facilities as follows: (1) calf rearing (enrollment to ～13 wk of age) and (2) grazier, after 13 wk until 22 mo of age. All heifers wore a collar with an activity sensor to monitor estrus events starting at 8 mo of age, and we collected weekly blood samples when individual heifers reached 190 kg of body weight (BW) to measure plasma progesterone concentrations. Puberty was characterized by plasma progesterone concentrations >1 ng/mL in at least 2 of 3 successive weeks. Date of puberty was defined when the first of these samples was >1 ng/mL. Heifers were seasonally bred for 98 d starting at ～14 mo of age. Transrectal ultrasound was used to confirm pregnancy and combined with activity data to estimate breeding and pregnancy dates. We measured BW every 2 wk, and body condition and stature at 6, 9, 12, and 15 mo of age. The significant FertBV by day interaction for BW was such that the NEG heifers had increasingly greater BW with age. This difference was mirrored with the significant FertBV by month interaction for average daily gain, with the NEG heifers having a greater average daily gain between 9 and 18 mo of age. There was no difference in heifer stature between the POS and NEG heifers. The POS heifers were younger and lighter at puberty, and were at a lesser mature BW, compared with the NEG heifers. As a result, 94 ± 1.6% of the POS and 82 ± 3.2% of the NEG heifers had reached puberty at the start of breeding. The POS heifers were 20% and 11% more likely to be pregnant after 21 d and 42 d of breeding than NEG heifers (relative risk = 1.20, 95% confidence interval of 1.03–1.34; relative risk = 1.11, 95% confidence interval of 1.01–1.16). Results from this experiment support an association between extremes in genetic merit for fertility base on cow traits and heifer reproduction. Our results indicate that heifer puberty and pregnancy rates are affected by genetic merit for fertility traits, and these may be useful phenotypes for genetic selection.     

Sequestration of zinc from zinc oxide nanoparticles and life cycle effects in the sediment dweller amphipod Corophium volutator

We studied the effects of ZnO nanoparticles [ZnO NPs, primary particle size 35 ± 10 nm (circular diameter, TEM)], bulk [160 ± 81 nm (circular diameter, TEM)], and Zn ions (from ZnCl(2)) on mortality, growth, and reproductive endpoints in the sediment dwelling marine amphipod Corophium volutator over a complete lifecycle (100 days). ZnO NPs were characterized by size, aggregation, morphology, dissolution, and surface properties. ZnO NPs underwent aggregation and partial dissolution in the seawater exposure medium, resulting in a size distribution that ranged in size from discrete nanoparticles to the largest aggregate of several micrometers. Exposure via water to all forms of zinc in the range of 0.2-1.0 mg L(-1) delayed growth and affected the reproductive outcome of the exposed populations. STEM-EDX analysis was used to characterize insoluble zinc precipitates (sphaerites) of high sulfur content, which accumulated in the hepatopancreas following exposures. The elemental composition of the sphaerites did not differ for ZnO NP, Zn(2+), and bulk ZnO exposed organisms. These results provide an illustration of the comparable toxicity of Zn in bulk, soluble, and nanoscale forms on critical lifecycle parameters in a sediment dwelling organism.     

Use of solution crystallization analysis by laser light scattering for studying the solution crystallization of various Ziegler–Natta‐catalysed polypropylenes

Solution crystallization analysis by laser light scattering (SCALLS) involves the observation of the scattering of diode mercury laser lamp light after it passes through a polymer solution. An increase in turbidity occurs when the hot polymer solution is cooled and the polymer starts to crystallize out of solution. This causes a decrease in the amount of laser light that can pass through the solution and an increase in the amount of scattered light. The reverse of this process leads to the turbidity decreasing with an increase in temperature. According to this concept, it is possible to follow the solution crystallization of various polypropylenes under controlled cooling. In this study, SCALLS was able to differentiate between different isotactic and syndiotactic polypropylenes with similar chemical structures, but different tacticity and molecular weights. Furthermore, SCALLS provided good crystallization information that is similar to that from crystallization analysis fractionation and temperature rising elution fractionation. In addition, SCALLS can be used as a quantitative tool for the measurement of weight fractions during dissolution. © 2014 Society of Chemical Industry     

Synthesis and Characterization of Poly[bis(ethyl salicylate)phosphazenes] and Poly[bis(ethyl salicylate diethylamino)phosphazenes] and Their Hydrolytic Degradation

The polydichlorophosphazenes were synthesized from hexachlorocyclotriphosphazenes by ring opening polymerization in the presence of AlCl₃ as a catalyst. Poly[bis(ethyl salicylate)phosphazenes] (PESP) and poly[bis(ethyl salicylate diethylamino)phosphazenes] (PESDEAP) were synthesized via macromolecular substitution reactions using ethyl salicylate and (or) diethylamine as side groups. The synthesis results were proved by nuclear magnetic resonance (¹H NMR, and ³¹P NMR) and gel permeation chromatography. In addition, the hydrolytic degradation of PESP and PESDEAP was investigated at constant temperature in neutral medium.     

Investigation of non-Newtonian flow characterization and rheology of heavy crude oil

The heavy crude oil exhibits a non-Newtonian shear thinning behavior over the examined shear rate. The viscosity of the heavy crude oil decreases about 15.6% when the temperature increased from 30 to 60°C. Heavy crude oil was blended with the aqueous solution of surfactant and saline water in different volumetric proportions of NaCl, and Na₂CO₃ solution mixtures. The addition of 50% of the mixture to the heavy crude oil causes a strong reduction in the viscosity, about 67.5% at 60°C. The heavy crude oil fits the Power law model since it has the lowest average absolute percent error of 0.0291. The flow behavior index of the heavy crude oil reaches a value of 0.9305 at a temperature of 30°C and it increases to 0.9373 when the temperature raises 60°C, while the consistence coefficient decreases from 2.8811 to 2.3558.     

Estimation of the Stress-Strength Reliability for Exponentiated Pareto Distribution Using Median and Ranked Set Sampling Methods

In reliability analysis, the stress-strength model is often used to describe the life of a component which has a random strength (X) and is subjected to a random stress (Y). In this paper, we considered the problem of estimating the reliability R=P [Y<X] when the distributions of both stress and strength are independent and follow exponentiated Pareto distribution. The maximum likelihood estimator of the stress strength reliability is calculatedunder simple random sample, ranked set sampling and median ranked set sampling methods. Four different reliability estimators under median ranked set sampling are derived. Two estimators are obtained when both strength and stress have an odd or an even set size. The two other estimators are obtained when the strength has an odd size and the stress has an even set size and vice versa. The performances of the suggested estimators are compared with their competitors under simple random sample via a simulation study. The simulation study revealed that the stress strength reliability estimates based on ranked set sampling and median ranked set sampling are more efficient than their competitors via simple random sample. In general, the stress strength reliability estimates based on median ranked set sampling are smaller than the corresponding estimates under ranked set sampling and simple random sample methods.     

Phase-Field Modeling of Sigma-Phase Precipitation in 25Cr7Ni4Mo Duplex Stainless Steel

Phase-field modeling is used to simulate the formation of sigma phase in a model alloy mimicking a commercial super duplex stainless steel (SDSS) alloy, in order to study precipitation and growth of sigma phase under linear continuous cooling. The so-called Warren–Boettinger–McFadden (WBM) model is used to build the basis of the multiphase and multicomponent phase-field model. The thermodynamic inconsistency at the multiple junctions associated with the multiphase formulation of the WBM model is resolved by means of a numerical Cut-off algorithm. To make realistic simulations, all the kinetic and the thermodynamic quantities are derived from the CALPHAD databases at each numerical time step, using Thermo-Calc and TQ-Interface. The credibility of the phase-field model is verified by comparing the results from the phase-field simulations with the corresponding DICTRA simulations and also with the empirical data. 2D phase-field simulations are performed for three different cooling rates in two different initial microstructures. A simple model for the nucleation of sigma phase is also implemented in the first case. Simulation results show that the precipitation of sigma phase is characterized by the accumulation of Cr and Mo at the austenite-ferrite and the ferrite-ferrite boundaries. Moreover, it is observed that a slow cooling rate promotes the growth of sigma phase, while a higher cooling rate restricts it, eventually preserving the duplex structure in the SDSS alloy. Results from the phase-field simulations are also compared quantitatively with the experiments, performed on a commercial 2507 SDSS alloy. It is found that overall, the predicted morphological features of the transformation and the composition profiles show good conformity with the empirical data.