What physical phenomena can be neglected when modelling concrete at high temperature? A comparative study. Part 2: Comparison between models

The paper deals with modelling of hygro-thermal performance and thermo-chemical degradation of concrete exposed to high temperature. Several possible simplifications in modelling of heat and mass transport phenomena in heated concrete are considered and their effect on the results of numerical simulations is analyzed.In part I of the companion paper, the physical phenomena, and heat and mass flux and sources in a concrete element were studied, both during slow and fast heating process, to examine the relative importance of different flux components. Then, the mathematical model of concrete at high temperature, developed by Authors in the last 10 years, was briefly presented and for the first time all the constitutive relationships of the model are summarized and discussed in detail. Finally, the method of numerical solution of the model equations was thoroughly presented.In this part of the paper a brief literature review of the existing mathematical models of concrete at high temperature and a summary of their main features and physical assumptions is presented first. Then, extensive numerical study is performed with several simplified models, neglecting a chosen physical phenomenon or flux component, to evaluate a difference between the results obtained with the simplified models and with the reference model. The study concerns hygric, thermal and degradation performance of 1-D and 2-D axisymmetric concrete elements during fast and slow heating. The analysis will allow us to indicate which simplifications in modeling of concrete at high temperature are practically and physically possible, without generating excessive differences of the results with respect to the full reference model.     

Model of gas-coal medium with a sorption phenomenon

Constitutive equations of a gas-coal two-phase medium with a local mass exchange due to a sorption-desorption phenomenon are presented. The equations have been deduced taking advantages of the theory of mixtures. Parameters of the constitutive equations have been calculated on the basis of results of laboratory tests published in recent papers. The governing set of equations of the theory is introduced and results of a sample calculation are presented.     

Minimal set of molecule-adapted atomic orbitals from maximum overlap criterion

The criterion of maximum overlap with the canonical free-atom orbitals is used to construct a minimal set of molecule-intrinsic orthogonal atomic orbitals that resemble the most their promolecular origins. Partial atomic charges derived from population analysis within representation of such molecule-adopted atomic orbitals are examined on example of first-row hydrides and compared with charges from other methods. The maximum overlap criterion is also utilized to approximate the exact free-atom orbitals obtained from ab initio calculations in any arbitrary basis set and the influence of the resulting fitted canonical atomic orbitals on properties of molecule-adopted atomic orbitals is briefly discussed.     

Synthesis of Phosphorylated Enaminoketones and Their Application in the Preparation of Trifluoromethyl-Functionalized 2-Phosphonopyrroles

Abstract

New trifluoromethyl-functionalized 2-phosphonopyrroles were obtained by 5-exotrig cyclization of trifluoromethyl and phosphonyl functionalized enaminoketones.

GRAPHICAL ABSTRACT      

Applicability of Gd-doped BaZrO3, SrZrO3, BaCeO3 and SrCeO3 proton conducting perovskites as electrolytes for solid oxide fuel cells

Four proton conducting oxides of perovskite structure: BaZrO₃, SrZrO₃, BaCeO₃ and SrCeO₃ doped with 5 mol.% of gadolinium are compared in terms of crystal structure, microstructure, sinterability, water sorption ability, ionic transference number, electrical conductivity and stability towards CO₂. Relations between proton conductivity, structural and chemical parameters: pseudo-cubic unit cell volume, lattice free volume, tolerance factor, crystal symmetry and electronegativity are discussed. The grain boundary resistance is shown to be the limiting factor of total proton-conductivity for the materials examined. The highest proton conductivity was observed for BaCeO₃, however, it turned out to be prone to degradation in CO₂-containing atmosphere and reduction at high temperatures. On the other hand, Ba and Sr zirconates are found to be more chemically stable, but exhibit low electrical conductivity. Electrical conductivity relaxation upon hydration is used to calculate proton diffusion coefficient. Selected materials were tested as electrolytes in solid oxide fuel cells.      

Synthesis of phosphorylated isoindolinone derivatives

The synthesis of diethyl [2-(2-alkyl-3-oxo-2,3-dihydro-1H-isoindol-1-yl)ethyl]phosphonates and diethyl [3-(2-alkyl-3-oxo-2,3-dihydro-1H-isoindol-1-yl)propyl]phosphonates, via metallation (sec-BuLi) of N-substituted isoindolin-1-ones and then the reaction of the generated lithiated species 4 with diethyl vinylphosphonate or diethyl 3-bromopropylphosphonate, respectively, is described.     

Densities,Excess Molar Volumes,and Thermal Expansion Coefficients of Aqueous Aminoethylethanolamine Solutions at Temperatures from 283.15 to 343.15 K

The densities of aqueous mixtures of aminoethylethanolamine (CAS #000111-41-1) were measured over the entire compositional range at temperatures of 283.15–343.15 K. The results of these measurements were used to calculate excess molar volumes and isobaric thermal expansion coefficients, and partial molar and apparent molar volumes and excess isobaric thermal expansion coefficients were subsequently derived. The excess molar volumes were correlated as a function of the mole fraction using the Redlich–Kister equation. Temperature dependences of the Redlich–Kister coefficients are also presented. The partial molar volumes at infinite dilution of AEEA in water were determined using two different methods. In addition, the solution density was correlated using a Joubian–Acree model. Aqueous solutions of AEEA exhibit similar properties to the aqueous solutions of other alkanolamines (like monoethanolamine) used in acid gas sweetening.     

Flavonoid Preparations from Taraxacum officinale L. Fruits—A Phytochemical,Antioxidant and Hemostasis Studies

Dandelion (Taraxacum officinale L.) roots, leaves, and flowers have a long history of use in traditional medicine. Compared to the above organs, dandelion fruits are the least known and used. Hence, the present paper was aimed at the phytochemical analysis of T. officinale fruit extract and estimating its antiradical, antiplatelet, and antioxidant properties related to hemostasis. Methanolic extract of fruits (E1), enriched with polyphenols (188 mg gallic acid equivalents (GAE)/g), was successfully separated into cinnamic acids (E2; 448 mg GAE/g) and flavonoids (E3; 377 mg GAE/g) extracts. Flavonoid extract was further divided into four fractions characterized by individual content: A (luteolin fraction; 880 mg GAE/g), B (philonotisflavone fraction; 516 mg GAE/g), C (flavonolignans fraction; 384 mg GAE/g), and D (flavone aglycones fraction; 632 mg GAE/g). High DPPH radical scavenging activity was evaluated for fractions A and B (A > B > Trolox), medium for extracts (Trolox > E3 > E2 > E1), and low for fractions C and D. No simple correlation between polyphenol content and antiradical activity was observed, indicating a significant influence of qualitative factor, including higher anti-oxidative effect of flavonoids with B-ring catechol system compared to hydroxycinnamic acids. No cytotoxic effect on platelets was observed for any dandelion preparation tested. In experiments on plasma and platelets, using several different parameters (lipid peroxidation, protein carbonylation, oxidation of thiols, and platelet adhesion), the highest antioxidant and antiplatelet potential was demonstrated by three fruit preparations–hydroxycinnamic acids extract (E2), flavonoid extract (E3), and luteolin fraction (A). The results of this paper provide new information on dandelion metabolites, as well as their biological potential and possible use concerning cardiovascular diseases.     

Water‐Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi‐Homogeneous Photocatalysis

Heptazine‐based polymeric carbon nitrides (PCN) are promising photocatalysts for light‐driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom‐up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi‐homogeneous conditions. The superior performance of water‐soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H₂O₂ production via reduction of oxygen accompanied by highly selective photooxidation of 4‐methoxybenzyl alcohol and benzyl alcohol or lignocellulose‐derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re‐dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.