Influence of Membrane Intrusion on Permeate‐Sided Pressure Drop During High‐Pressure Reverse Osmosis

By replacing thermal concentration processes, high‐pressure reverse osmosis has the potential to contribute to cost and energy savings regarding concepts for industrial water reuse. To provide a better understanding of the spiral‐wound element behavior during high‐pressure operation, this study focusses on the investigation of their performance by scrutinizing the crucial effect of the permeate‐sided pressure drop induced by membrane‐spacer interactions. The experiments show a considerable influence of membrane intrusion on the element performance with a strong dependence on the feed pressure.     

One‐Step Immobilization of Protein‐Encapsulated Core/Shell Particles onto Nanofibers

A novel method is described to functionalize nanofibers to form a nanocomposite with core/shell particles in order to control protein release. The nanocomposite is produced by electrically neutralizing negatively charged poly(lactic acid) nanofibers with positively charged poly[(lactic acid)‐co‐(glycolic acid)] particles via a one‐step electrohydrodynamic jetting process. The protein‐encapsulated core/shell particles exhibited no significant initial burst release or denaturation. The protein release profile was controlled by porosity and protein/polymer interactions. The method may be promising to engineer intelligent scaffolds that can fulfill the needs of biomimetic materials.

     

One‐Dimensional Modeling and Simulation of Bubble Column Reactors

Reactor models that feature a practical way to design bubble columns on the semi‐industrial or even industrial scale have been published only rarely in the usual scientific literature. Creating a one‐dimensional model in the equation‐oriented simulation software ASPEN Custom Modeler? (ACM), one can reach a compromise between model precision and modeling – i.e. computational power – based on correlations selected specifically for the application in question. The model quantitatively describes, with sufficient accuracy, the processes in a bubble column reactor. The paper discusses investigations for designing a pilot plant reactor for hydrogenating 2‐ethylhexanal as an example of its application. Geometry and operating conditions were optimized, and the results are shown in the form of spatially resolved reaction and temperature profiles.     

One‐Pot Carbon Monoxide‐Free Hydroformylation of Internal Olefins to Terminal Aldehydes

A one‐step hydroformylation of mixtures of internal and terminal olefins yielding terminal aldehydes without the need for carbon monoxide has been developed. Treatment of the olefin mixtures with Rh catalysts and pinacolborane leads to isomerization and hydroboration in one step. Homologation and subsequent oxidation regiospecifically afford the terminal aldehyde. Good overall yields are obtained for all substrates examined.     

Synthesis of 2,4,6,8,10,12‐Hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane Using Melaminium‐tris(hydrogensulfate) by a Simple One‐Pot Nitration Procedure

A highly efficient protocol for the synthesis of 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane (CL‐20) in the presence of melaminium‐tris(hydrogen sulfate) as a solid acid is described.     

Using NSGA‐II and TOPSIS Methods for Interior Ballistic Optimization Based on One‐Dimensional Two‐Phase Flow Model

In order to meet the design demands of new gun systems or new types of projectiles, the interior ballistic charge design seems especially important. In this paper, a one‐dimensional two‐phase flow model is presented. The model describes the transient combustion of granular propellants in a gun, and pressure waves are considered as an objective. This study adopts a hybrid method to solve the problem. In the first stage, the non‐dominated sorting genetic algorithm (NSGA‐II) with “a “filter” is employed to approximate a set of Pareto‐optimal solutions. In the subsequent stage, a multi‐attribute decision‐making (MADM) approach is adopted to rank these solutions from the best to the worst. The ranking of Pareto‐optimal solutions is based on the technique ordered preference by similarity to ideal solution (TOPSIS) method. In TOPSIS method each objective needs a corresponding weight coefficient, and a practical problem is introduced. Both the entropy method and linear analysis method are adopted to get two sets of weights for the objectives, respectively. The two pairs of final, best compromise solutions are compared for satisfying the designer’s aim. For the analysis of the results, a two‐phase flow interior ballistic model for design optimization is established, and the hybrid approach could get a reasonable design scenario.     

Prediction of Gas‐Phase Adsorption Isotherms Using Neural Nets

This study investigated a number of models (the modified Sips', Dubinin‐Astakhov's, VSM theory, the generalized Khan et al.'s model and a simple artificial neural network (ANN)) to predict the effect of temperature on equilibrium adsorption of hydrocarbon gases and vapors on activated carbon. Published data on the adsorption of methane, ethane and propane on activated carbon at 311 K to 505 K were used to estimate the parameters of the conventional models and train the network. Then, the conventional models and the ANN were used to predict the isotherm at a single temperature for each adsorbate, and these results were compared with experimental data. It was found that the ANN model had a lower mean relative error than the conventional models.     

Experimental Study and DEM Simulation of Micro–Macro Behavior of TATB Granules During Compaction Using X‐ray Tomography

In this study, a noninvasive experimental method and a discrete element method (DEM) model were used to investigate the micro–macro behavior of TATB granules including global deformations, contact forces, stress distributions, local coordination number, local pore ratio, particle kinematics, and granule displacement during compacting process. The TATB granule deformation and structural evolution during compaction process were studied by X‐ray tomography and the deformation characteristics of deformable material. The size and number of granules with different sizes were determined from the CT images. The digital microstructure can be directly used for the numerical simulation setup. The DEM method was used for the numerical simulation of TATB granules during compaction. The contact forces and displacement vectors in compaction process were obtained. The behaviors and stress distributions at different pressures were also derived from the simulation. This study evaluated the possibility to better describe the behaviors of TATB granules.     

One‐Pot Synthesis of Submicrometer‐Sized Ce:YAG Spherical Particles by Solvothermal Process Using Alcohol Solvents

A rapid synthesis method for preparing homogeneous and submicrometer‐sized cerium‐doped yttrium aluminum garnet (Ce:YAG) particles was proposed in this work. Instead of precipitating the YAG amorphous precursor prior to the solvothermal process, cerium, yttrium, and aluminum nitrates were dissolved in alcoholic solvents to form transparent and clear solutions that were directly transferred into the stainless autoclave to undergo the solvothermal reaction. Four different alcohol solvents, that is, ethanol, 2‐propanol, 2‐butanol, and tert‐butanol, were used as the reaction medium. The crystallization mechanisms in correlation with the alcohol solvent properties, such as the supercritical point and the dielectric constant, were discussed. The interaction between the alcohol solvent and the precursor salts were also investigated. Well‐dispersed and spherical Ce:YAG particles in size ranging from 200 to 350 nm were obtained in one pot via solvothermal reaction at 285°C from 5 to 8 h.     

Olive Oil Quality and Sensory Changes During House‐Use Simulation and Temporal Assessment Using an Electronic Tongue

During domestic usage, olive oil bottle manipulation may lead to a quality decrease due to agitation and oxygenation. Therefore, assessing the domestic consumption time period during which the initial quality grade is retained may allow including this information as a recommendation, ensuring olive oil consumers’ satisfaction. Temporal changes of physicochemical, chemical, and sensory parameters of extra‐virgin olive oils (EVOO) were monitored during 1‐month simulated house‐use conditions. It was observed that K₂₃₂ (R‐Pearson ≥+0.81) and ΔK increased resulting in a significant olive oil quality decrease from EVOO (during the initial 21 days of simulated usage) to lampante olive oil (after 28 days of simulated usage) as well as the appearance of rancid sensation. As lampante olive oils cannot be commercialized, it is pertinent to establish olive oil shelf life under usual home‐use conditions. Principal component analysis allowed grouping the olive oils according to home‐use time period and how bottles are stored after their first opening, showing that the overall olive oil physicochemical and sensory characteristics changed with the domestic‐use time period. Finally, a potentiometric electronic tongue coupled with linear discriminant analysis was used to discriminate olive oils according to the domestic‐use time period (leave‐one‐out cross‐validation sensitivities ≥95%). Thus, this device could be used to indirectly assess the quality of the remaining bottled olive oil by establishing for how long an olive oil bottle has been used under domestic conditions.     

Diffusion of One‐ and Two‐Component Fluids into Polymeric Membranes

The starting point of this paper is a model of the non‐Fickian diffusion of a simple fluid into a polymeric medium that has been introduced in El Afif and Grmela (2002). The model is extended to a mixture consisting of two simple fluids and one polymeric medium. The effects of the polymeric medium on diffusion are included in the formulations through the use of relative momenta playing the role of internal variables. In ternary mixtures, new phenomena arise due to cross‐coupling effects. As a consequence, the single diffusion Deborah number in binary mixtures becomes a 2 × 2 matrix in ternary mixtures. Two specific examples for which experimental data are available are investigated in detail.     

Improved Prediction of Young's Modulus of Fluorine‐Containing Glasses Using MAS‐NMR Structural Data

The model developed by Makishima and Mackenzie (M–M) may yield reasonable estimates for the E‐modulus of a range of glasses. In the M–M model the bonding enthalpy and packing densities present in the compounds that form the glass are taken as input for the calculation. This study shows that a more accurate estimate can be obtained by incorporating in the model structural information from MAS‐NMR data. Specifically, we have determined by means of the impulse excitation technique (IET) the E‐modulus for ionomer glasses with composition 4.5SiO₂–3Al₂O₃–1.5P₂O₅–3MO–2MF₂, where M denotes the alkaline earth metal (M = Mg, Ca, Sr, or Ba). The MAS‐NMR structural analysis shows that substitution of calcium by barium or strontium results in a disrupted network, whereas magnesium leads to a more packed network. In this study we will show how a higher coordination state of the aluminum as determined by ²⁷Al MAS‐NMR can be taken into account in the model. This leads to rather small corrections of the estimates for these particular glasses. In contrast, the ¹⁹F MAS‐NMR study shows the presence of Al–F–M(n) or Al–F and Si–F–M(n) types of environment in the glass network. Al–F and Si–F bonds are not accounted for in the E‐modulus estimate by the M–M model. We will show how by incorporating the new bonding of F with Al and Si a significantly improved estimate of the E‐modulus is obtained compared with the original model.     

Effect of Catalyst Supports on Water‐Gas Shift Reaction at Ultrahigh Temperatures Using Syngas

Monometallic and bimetallic catalysts (Pt, Ni, and Pt‐Ni) with single support (Al₂O₃, TiO₂) and composite support (CeO₂/Al₂O₃, CeO₂/TiO₂) were prepared and tested for water‐gas shift reaction in a tubular quartz reactor. Syngas and steam with different steam‐to‐carbon ratios served as feedstock. The operating pressure was fixed while the reaction temperature was varied. The measured results indicated that the monometallic Ni/Al₂O₃ catalyst exhibits the lowest CO conversion and H₂ yield as compared with other catalysts. About the same CO conversion can be obtained from Pt and Pt‐Ni catalysts with single or composite support. However, higher H₂ yield can be achieved from the TiO₂‐supported catalyst compared with those supported by Al₂O₃. The experimental data also indicated that good thermal stability can be reached for the Pt‐based catalysts studied.     

Moisture Profiles Determination During Convective Drying Using X‐Ray Microtomography

The knowledge of internal moisture profiles which develop during drying is essential for model validation purposes, but they are difficult to determine experimentally. This paper shows that X‐ray microtomography, together with image analysis, provides an accurate, non destructive and easy to use technique to determine moisture profiles. Results reported concern the drying of wastewater sludges whose management is becoming a real environmental challenge. An analysis of the development of moisture gradients at the sample external wall shows an influence of drying operating conditions. Finally, mass diffusion coefficients are estimated from the knowledge of both the moisture gradients and the drying flux.     

The Microstructure of TATB‐Based Explosive Formulations During Temperature Cycling Using Ultra‐Small‐Angle X‐Ray Scattering

TATB (1,3,5 triamino‐2,4,6‐trinitrobenzene), an extremely insensitive explosive, is used both in polymer‐bound explosives (PBXs) and as an ultra‐fine pressed powder (UFTATB). Many TATB‐based explosives, including LX‐17, a mixture of TATB and Kel‐F 800 binder, experience an irreversible expansion with temperature cycling known as ratchet growth. Additional voids, with sizes hundreds of nanometers to a few micrometers, account for much of the volume expansion. Measuring these voids is important feedback for hot‐spot theory and for determining the relationship between void size distributions and detonation properties. Also, understanding mechanisms for ratchet growth allows future choice of explosive/binder mixtures to minimize these types of changes, further extending PBX shelf life. This paper presents the void size distributions of LX‐17, UFTATB, and PBXs using commercially available Cytop M, Cytop A, and Hyflon AD60 binders during temperature cycling between −55 and 70 °C. These void size distributions are derived from ultra‐small‐angle X‐ray scattering (USAXS), a technique sensitive to structures from about 2 nm to about 2 μm. Structures with these sizes do not appreciably change in UFTATB. Compared to TATB/Kel‐F 800, Cytop M and Cytop A show relatively small increases in void volume from 0.9 to 1.3% and 0.6 to 1.1%, respectively, while Hyflon fails to prevent irreversible volume expansion (1.2–4.6%). Computational mesoscale models combined with experimental results indicate both high glass transition temperature as well as TATB binder adhesion and wetting are important to minimize ratchet growth.     

Iterative One‐Pot α‐Glycosylation Strategy: Application to Oligosaccharide Synthesis

Based on the combined use of dimethylformamide (DMF) modulation and neighboring group participation, three iterative one‐pot α‐glycosylation methods, i.e., one‐pot (α,α)‐, one‐pot (β,α)‐, and one‐pot (α,β)‐glycosylations, were developed. These methods are applicable to a range of thioglycosyl donors, confer stereocontrol in α‐/β‐glycosidic bond formation, and thus provide for rapid access to oligosaccharides with various permutations of anomeric configurations. The utility of these one‐pot glycosylation methods is demonstrated in the synthesis of eight non‐natural and natural oligosaccharide targets, including the core 1 serine conjugate, core 8 serine conjugate, the D ‐Gal‐α(1→3)‐D ‐Glc‐α(1→3)‐L ‐Rha trisaccharide unit of the cell wall component in Streptococcus pneumoniae, and the D ‐Glc‐α(1→2)‐D ‐Glc‐α(1→3)‐D ‐Glc trisaccharide terminus of the N‐linked glycan precursor. Confirmation of the anomeric configurations of these oligosaccharides is evidenced by ¹H, ¹³C, ¹³C‐non‐proton decoupling, and heteronuclear correlation 2D NMR experiments. Global deprotection of selected oligosaccharide targets is illustrated.