A new Lagrangian decomposition approach applied to the integration of refinery planning and crude-oil scheduling

The aim of this paper is to introduce a methodology to solve a large-scale mixed-integer nonlinear program (MINLP) integrating the two main optimization problems appearing in the oil refining industry: refinery planning and crude-oil operations scheduling. The proposed approach consists of using Lagrangian decomposition to efficiently integrate both problems. The main advantage of this technique is to solve each problem separately. A new hybrid dual problem is introduced to update the Lagrange multipliers. It uses the classical concepts of cutting planes, subgradient, and boxstep. The proposed approach is compared to a basic sequential approach and to standard MINLP solvers. The results obtained on a case study and a larger refinery problem show that the new Lagrangian decomposition algorithm is more robust than the other approaches and produces better solutions in reasonable times.     

Synthesis of ‘ready-to-adsorb’ polymeric nanoshells for magnetic iron oxide nanoparticles via atom transfer radical polymerization

Polymer-magnetite nanoparticle complexes that respond to both magnetic fields and to temperature have been demonstrated. Novel alkyl halide-functional bis(diethylphosphonate) esters were prepared and utilized as initiators for polymerizing N-isopropylacrylamide by controlled atom transfer radical polymerization. The phosphonate esters were removed after polymerization to afford poly(N-isopropylacrylamide) with a bis(phosphonic acid) moiety precisely placed at one terminus. The bis(phosphonic acid) endgroups were adsorbed onto magnetite nanoparticles to yield nanoscale complexes that were stable against any polymer desorption and that were colloidally-stable in physiological media. Thus, the bis(phosphonate) endgroup provides a robust anchoring moiety onto the magnetite. Hydrodynamic sizes of the complexes were predicted with a density distribution model and using the measured sizes of the magnetite cores. Good agreement between the measured and predicted hydrodynamic sizes suggested that the complexes were primarily discrete, non-agglomerated nanoparticles. The complexes exhibited thermosensitive aggregation behavior near the lower critical solution temperature of the poly(N-isopropylacrylamide) component.     

Potential of ionic liquids for VOC absorption and biodegradation in multiphase systems

This work aims to evaluate the feasibility of using imidazolium ionic liquids (ILs) in the design of multiphase bioreactors for the removal of volatile organic compounds (VOCs). The IL affinity for three model VOCs (dimethyl sulfide, dimethyl disulfide and toluene) was evaluated by means of the dimensionless partition coefficient (K). It was observed that ILs showed K values comparable to typical liquid solvents used in multiphase bioreactors for VOC biodegradation (K values ranged from 0.009 to 0.011, 0.0012 to 0.0013 and 0.00061 to 0.00096 for dimethyl sulfide, dimethyl disulfide and toluene, respectively). Toxicity tests showed that both ILs at concentrations of 5% and 10% (v/v) inhibited the glucose uptake of an activated sludge during approximately 24 h. After such lag period, the microorganisms were able to recover its metabolic activity. However, VOC biodegradation experiments showed that ILs at 5% (v/v) were toxic for the activated sludge and a toxic synergistic effect of the IL–VOC combination likely occurred. After acclimation to the target VOCs, only the toluene biodegradation capacity was significantly increased in the presence of ILs. These toxic effects represent a key drawback for the potential of IL-based multiphase systems devoted to VOC biodegradation. Therefore, this study suggests that microbial acclimation only to the VOCs is not enough to get an efficient biodegradation in multiphase systems including ILs as non-aqueous phases.     

Modelling the solubility in Bayer liquors: A critical review and new models

An accurate and tractable model of solubility is a pre-requisite for any careful study of precipitation. Reviewing the abundant literature on the sodium aluminate solutions and Bayer Liquor, the authors point out the need for a new model for the apparent solubility of aluminium in actual Bayer Liquors and propose such a model, based on the well established Wesolowski's expression for the infinite dilution solubility and extended Debye–Hückel expression including a large empirical b I term for the “activity coefficient effect”. They suggest a chemical interpretation for this feature.     

Elaboration and Characterization of Advanced Biobased Polyurethane Foams Presenting Anisotropic Behavior

Biobased and open cell polyurethane (PU) foams are produced from a synthesized sorbitol‐based polyester polyol. Different formulations are developed with various blowing agent systems (chemical vs physical blowing). Synthetized foams are fully characterized and compared. The cell morphology is carefully investigated by tomography and scanning electron microscopy. The chemical nature of the primary compounds, foaming kinetics, density, thermal behavior, and conductivity are fully studied, with also the main transition materials temperatures. It is shown that blowing agents especially impact the foaming kinetics. In the case of chemically blowing foams, higher foaming rate and temperatures are obtained. The mechanical behavior is particularly analyzed using quasi‐static compression tests, according two main axes compared to the rise direction. A direct relationship is observed between the formulation, foam structure, foam morphology, and corresponding mechanical properties. Results clearly highlight unexpected properties of biobased PU foams with unveil anisotropic mechanical properties.     

An Advanced GAP/AN/TAGN Propellant. Part I: Ballistic Properties

A solid rocket propellant based on glycidyl azide polymer (GAP) binder plasticized with nitrate esters and oxidized with a mixture of ammonium nitrate (AN) and triaminoguanidine nitrate (TAGN) was formulated and characterized. Non‐lead ballistic modifiers were also included in order to obtain a propellant with non‐acidic and non‐toxic exhaust. This propellant was found to exhibit a burning rate approximately twice that of standard GAP/AN propellants. The exponent of the propellant is high compared to commonly used composite propellants but is still in the useable range at pressures below 13.8 MPa. This propellant may present a good compromise for applications requiring intermediate burn rate and impulse combined with low‐smoke and non‐toxic exhaust.     

Sitona lineatus Host-Plant Odors and Their Components: Effect on Locomotor Behavior and Peripheral Sensitivity Variations

Adult Sitona lineatus L., (Coleoptera: Curculionidae) feed on the leaves of various species of leguminous plants, and females lay in the vicinity of pea plants, the roots of which are eaten by the larvae. A study of the volatiles from several legumes and of the response of S. lineatus individuals to these substances was undertaken using two complementary techniques: behavioral, to study the locomotory orientation; and electrophysiological, using electroantennography (EAG). Four volatile compounds, cis-3-hexen-1-ol, 2-hexenal, cis-3-hexen-1-yl acetate, and 3-octanone, were identified from pea, vetch, clover, and lucerne, by coupled gas chromatography–mass spectrometry (GC-MS) and coupled gas chromatography–infrared spectrometry (GC-IR). After emergence from July to mid-November, the imago display high response to the odor of pea and some other leguminous plants. A second period of enhanced sensitivity was observed during crop colonization from March to May. High EAG response to pea odor and cis-3-hexen-1-yl acetate was correlated with periods of enhanced locomotory orientation during these months. Experimental results indicate that cis-3-hexen-1-yl acetate could play a key role in discriminating pea among other acceptable leguminous species.     

Application of the Electrodiffusion Method to Measure Wall Shear Stress: Integrating Theory and Practice

The electrodiffusion method has been used in fluid dynamic research for the past 50 years. It allows the measurement of wall shear stress, a crucial parameter, e.g., for the cleaning of membrane modules used in water filtration. Various authors have published articles dealing with the theory behind this technique. But no paper collects all the knowledge assembled over five decades of application. Here, comprehensive summary of the theory of steady flow, unsteady flow, and transient voltage step experiments is given. Factors influencing the accuracy of the measurements are discussed. Furthermore, a new approach to calibrate the system from voltage step experiments is introduced, and practical issues related to its application in flow measurements are discussed for an exemplary signal response to a near‐wall flow.     

Optimization of the spark plasma sintering processing parameters affecting the properties of polyimide

The present study deals with the optimization of polyimide (PI) mechanical properties, obtained by Spark Plasma Sintering (SPS), by using a method combining Design of Experiments (DOE) with physical, structural, and mechanical characterizations. The effects of SPS parameters such as temperature, pressure, dwell time, and cooling rate on the density, mechanical properties, and structure of PI were investigated. The experimental results revealed that the mechanical properties of the material were optimized by raising the sintering temperature up to 350°C. The optimized SPS processing parameters were a temperature of 350°C, a pressure of 40 MPa, and a dwell time of 5 min. Under these conditions, a relative density of 99.6% was reached within only a few minutes. The corresponding mechanical properties consisted of Young's modulus of 3.43 GPa, a Shore D hardness of 87.3, and a compressive strength of 738 MPa for a maximum compressive strain of 61.8%. Moreover, when working at 320°C and at 100 MPa, an increase in the dwell time was necessary to enhance the properties. Contrary to the other parameters, the cooling rate appeared to be a non‐significant parameter. Finally, correlations between the PI structure and the mechanical properties were made to demonstrate the densification mechanisms. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41542.     

Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.