Chemical reactivity of mineral aggregates in aqueous solution: relationship with bitumen emulsion breaking

This paper reports a study on chemical reactivity of gneiss, diorite and limestone aggregates in aqueous solution. The originality of this study is that it extended to very short times (less than 1440 min). Rise in pH tests was implemented and dissolution kinetics was analysed. The results showed that calcium was the major element released by the aggregates. It has also been found that dissolution had an influence on the final morphology of aggregates. Polyamine emulsifier adsorption onto aggregates has been assessed using electrophoresis. Finally, the rise in pH and electrophoretic tests were compared to the breaking test traditionally performed to characterise bitumen emulsions. It was found that breaking values were controlled by both the surface area and the surface charge of the particles. Results may be correlated to polyamine adsorption on aggregates. Adsorption seemed to be efficient for gneiss and diorite: at pH 2, their charge turned from slightly negative to highly positive. At this pH value, limestone particles were dissolved and polyamine adsorption must be less efficient than with gneiss and diorite, for which the emulsion breaking was facilitated by the high attraction of particles for the emulsifier, due to their negative surface charge.     

Convenient thionation of triglycerides with lawessons reagent

Thionation using the Lawesson’s reagent (LR) led to quantitative and selective replacement of carbonyl groups (C=O) with thionocarbonyl groups (C=S). Mixtures of thionotriglycerides were obtained by reaction of 2,4-bis (p-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide in suspension with triglycerides (TG). With a molar ratio (LR)/(TG)=3∶2, there was complete exchange of C=O with C=S in the carboxylic groups of the TG. The yield is over 90%. The two P=S ligands in the LR confer a double reactivity, producing a high power of thionation. Fourier transform infrared spectroscopy was employed for quantitative and qualitative characterization of the thionated TG and for monitoring the progress of partial or total thionation as conditioned by the molar ratios of the starting compounds. Thus, with molar ration LR/TG of 0.108, 0.36, and 0.72, we obtained around 6, 20, and 40% of C=O conversion, respectively.     

Kinetic study of liquid lipase-catalyzed glycerolysis of olive oil using Lipozyme TL 100L

Monoacylglycerol (MAG) and diacylglycerol (DAG) are two natural components found in most edible oils and fats. Conventional synthesis of MAG and DAG is usually conducted by glycerolysis of triacylglycerol (TAG) at high temperatures (above 200°C) in the presence of an alkaline catalyst. In this work, the synthesis of MAG and DAG using enzymatic glycerolysis of olive oil was investigated using Tween 80 as surfactant, n-butanol as co-surfactant and the novel lipase in free/liquid formulation Lipozyme TL 100L as catalyst. Experimental design was used to evaluate the effect of enzyme load and reaction temperature on the feedstock conversion. Enzyme load and system temperature were significant variables in the statistical design and the best condition was found at 35°C, 7.5 vol% of Lipozyme TL 100L and glycerol to oil volumetric ratio of 2:1 with conversion of TAG at approximately 98% after 2 h of process. A mathematical model based on the Ping-Pong Bi-Bi mechanism was used to describe the reaction kinetics. The model adequately described the behavior of the system and can be a useful tool for the design of reactors in larger scales.     

Milk fatty acids as possible biomarkers to early diagnose elevated concentrations of blood plasma nonesterified fatty acids in dairy cows

Most cows encounter a state of negative energy balance during the periparturient period, which may lead to metabolic disorders and impaired fertility. The aim of this study was to assess the potential of milk fatty acids as diagnostic tools of detrimental levels of blood plasma nonesterified fatty acids (NEFA), defined as NEFA concentrations beyond 0.6 mmol/L, in a data set of 92 early lactating cows fed a glucogenic or lipogenic diet and subjected to 0-, 30-, or 60-d dry period before parturition. Milk was collected in wk 2, 3, 4, and 8 (n = 368) and blood was sampled weekly from wk 2 to 8 after parturition. Milk was analyzed for milk fatty acids and blood plasma for NEFA. Data were classified as “at risk of detrimental blood plasma NEFA” (NEFA ≥0.6 mmol/L) and “not at risk of detrimental blood plasma NEFA” (NEFA <0.6 mmol/L). Concentrations of 45 milk fatty acids and milk fat C18:1 cis-9-to-C15:0 ratio were subjected to a discriminant analysis. Milk fat C18:1 cis-9 revealed the most discriminating variable to identify detrimental blood plasma NEFA. A false positive rate of 10% allowed us to diagnose 46% of the detrimental blood plasma NEFA cases based on a milk fat C18:1 cis-9 concentration of at least 230 g/kg of milk fatty acids. Additionally, it was assessed whether the milk fat C18:1 cis-9 concentrations of wk 2 could be used as an early warning for detrimental blood plasma NEFA risk during the first 8 wk in lactation. Cows with at least 240 g/kg of C18:1 cis-9 in milk fat had about 50% chance to encounter blood plasma NEFA values of 0.6 mmol/L or more during the first 8 wk of lactation, with a false positive rate of 11.4%. Profit simulations were based on costs for cows suffering from detrimental blood plasma NEFA, and costs for preventive treatment based on daily dosing of propylene glycol for 3 wk. Given the relatively low incidence rate (8% of all observations), continuous monitoring of milk fatty acids during the first 8 wk of lactation to diagnose detrimental blood plasma NEFA does not seem cost effective. On the contrary, milk fat C18:1 cis-9 of the second lactation week could be an early warning of cows at risk of detrimental blood NEFA. In this case, selective treatment may be cost effective.     

Emulsifying properties of β-lactoglobulin and Quillaja bark saponin mixtures: Effects of number of homogenization passes,pH, and NaCl concentration

The effects of number of homogenization passes, pH, and NaCl concentration on the formation and stability of oil-in-water emulsions comprising a mixture of a biosurfactant (Quillaja bark saponin) and a globular protein (β-lactoglobulin) were investigated. The emulsions were characterized as to visual appearance, droplet size, droplet surface charge, and rheology. The emulsions obtained by different conditions (4, 6, or 8 passes; pH 7, 8, or 9; and 0, 100, or 200 mmol L^?1 of NaCl) were polydisperse, presented relatively small average droplet sizes (z-average < 323 nm) as well as negative droplet charge (between –20 and –79.6 mV) in all evaluated conditions. Regardless of the number of homogenization passes, the emulsions exhibited low apparent viscosity and pseudoplastic behavior with small yield stress. Viscoelastic behavior was also observed, thus the emulsions were characterized as weak gels. Four homogenization passes were enough to obtain small droplets in the evaluated conditions. Droplet size was not significantly affected by NaCl concentration and pH (p > 0.05). On the other hand, the absolute ζ-potential values significantly decreased and increased upon increased NaCl content and pH, respectively. Regardless of the tested conditions, all emulsions had good stability against phase separation and droplet aggregation, since no significant changes in average droplet size were observed throughout storage (p > 0.05). In the presence of NaCl, in which droplet charge significantly decreased, emulsion was also stable. Thus, we can conclude that electrostatic repulsion as well as steric repulsion was responsible for stabilization.     

Borago officinalis oil: Fatty acid fractionation by immobilized Candida rugosa lipase

γ-Linolenic acid (Z,Z,Z-6,9,12-octadecatrienoic acid), a very important polyunsaturated fatty acid is found in the free fatty acid fraction prepared by the hydrolysis of borage oil. Our aim was to enrich this fraction in γ-linolenic acid using selective esterification. Candida rugosa lipase was used as catalyst after immobilization on the following ion-exchange resins: Amberlite IRC50, IRA35, IRA93, and Duolite A7, A368, A568. In every case, immobilization modified the lipae’s specificity: palmitic, stearic, oleic, and linoleic acids were preferentially esterified compared to γ-linolenic acid, thus allowing a γ-linolenic acid enrichment of 3.0.     

Prediction of corrosion-induced cover cracking in reinforced concrete structures

Usually, the time of repair/replacement of reinforced concrete structures due to corrosion is controlled by cracking of the concrete cover. Thus, it is important to be able to predict with sufficient accuracy the time from corrosion initiation to crack formation in the concrete cover. The paper presents a critical overview of existing empirical, analytical and numerical models for predicting the time to corrosion-induced cover cracking. A simple nonlinear finite element (FE) is then formulated and validated. The FE model is employed to investigate inaccuracies of analytical models arising due to simplified formulation of the nonlinear behaviour of concrete and inability to account for actual location of corroding reinforcing bars. Recommendations on the applicability of analytical models are provided. Finally, the FE model is used to estimate the amount of corrosion products penetrating into concrete pores and microcracks since this amount is an essential parameter for analytical and numerical models.     

A representative and comprehensive review of the electrical and thermal properties of polymer composites with carbon nanotube and other nanoparticle fillers

In this review we present the results of our literature investigation into the electrical and thermal properties of carbon nanotube polymer composites. A short selection of data relating to conductive polymer composites with various fillers is provided for comparison. The effects of filler properties such as type and size, the use of hybrid fillers, fabrication methods for polymer composites and the importance of the modeling of the electronic and thermal transport mechanisms are discussed, as are more general factors influencing the properties of these composites. This review represents a comprehensive survey and constructive study and should serve as a useful reference tool for industrial and academic researchers working in this field. © 2017 Society of Chemical Industry     

Model for thermodynamic point identification in laser cutting

In recent years, laser cutting has been introduced and developed to such an extent that it is now thought to be one of the leading and indispensable manufacturing tools. At the present time, dross‐free and accurately‐cut parts are basically regarded as the major targets to aim for, because the costs and efforts associated with dross removal by postprocessing cut parts are considerable. Therefore, control of dross formation during laser cutting is an important factor in maintaining edge quality. The initial aim of this paper is to describe the importance of physico‐mechanical material properties that need to be taken into account in modeling of laser material processing in order to control melting of the material.     

Heat and Mass Transfer in Capillary-Pumped Liquid Films in Square Cross-Section Minichannels

This study addresses heat and mass transfer during the vaporization of a liquid in a heated square cross-section mini-channel. A theoretical model is developed in steady state using the radius of curvature as a variable. One-dimensional simulations have been performed. An analysis of this model reveals that heat and mass transfer is governed by two main groups of non-dimensional numbers (i.e., Reynolds × Boiling and Weber × Boiling² numbers). Maps of heat transfer performance are thus proposed according to these non-dimensional numbers. A reduced model is finally derived, allowing the main parameters to be expressed (such as the extended meniscus length) analytically.