Preparative chromatographic separation of ternary mixtures : analysis of fractionation times and novel concepts

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2010

Development of Performance Properties of Ternary Mixtures and Concrete Pavement Mixture Design and Analysis (MDA): Effect of Paste Quality on Fresh and Hardened Properties of Ternary Mixtures, TPF-5(117), 2012

The purpose of this study was to investigate the effect of cement paste quality on the concrete performance, particularly fresh properties, by changing the water-to-cementitious materials ratio (w/cm), type and dosage of supplementary cementitious materials (SCM), and airvoid system in binary and ternary mixtures. In this experimental program, a total matrix of 54 mixtures with w/cm of 0.40 and 0.45; target air content of 2%, 4%, and 8%; a fixed cementitious content of 600 pounds per cubic yard (pcy), and the incorporation of three types of SCMs at different dosages was prepared. The fine aggregate-to- total aggregate ratio was fixed at 0.42. Workability, rheology, air-void system, setting time, strength, Wenner Probe surface resistivity, and shrinkage were determined. The effects of paste variables on workability are more marked at the higher w/cm. The compressive strength is strongly influenced by the paste quality, dominated by w/cm and air content. Surface resistivity is improved by inclusion of Class F fly ash and slag cement, especially at later ages. Ternary mixtures performed in accordance with their ingredients. The data collected will be used to develop models that will be part of an innovative mix proportioning procedure.

Development of Performance Properties of Ternary Mixtures: Field Demonstrations and Project Summary, TPF-5(117), 2012

Supplementary cementitious materials (SCM) have become common parts of modern concrete practice. The blending of two or three cementitious materials to optimize durability, strength, or economics provides owners, engineers, materials suppliers, and contractors with substantial advantages over mixtures containing only portland cement. However, these advances in concrete technology and engineering have not always been adequately captured in specifications for concrete. Users need specific guidance to assist them in defining the performance requirements for a concrete application and the selection of optimal proportions of the cementitious materials needed to produce the required durable concrete. The fact that blended cements are currently available in many regions increases options for mixtures and thus can complicate the selection process. Both Portland and blended cements have already been optimized by the manufacturer to provide specific properties (such as setting time, shrinkage, and strength gain). The addition of SCMs (as binary, ternary, or even more complex mixtures) can alter these properties, and therefore has the potential to impact the overall performance and applications of concrete. This report is the final of a series of publications describing a project aimed at addressing effective use of ternary systems. The work was conducted in several stages and individual reports have been published at the end of each stage.

The Use of Ternary Mixtures in Concrete, TPF-5(117), 2014

This manual is a summary of the findings of a comprehensive study. Its purpose is to provide engineers with the information they need to make educated decisions on the use of ternary mixtures for constructing concrete structures. It discusses the effects of ternary mixtures on fresh and hardened mixture properties and on concrete sustainability; factors that need to be considered for both structural and mixture design; quality control issues; and three example mixtures from constructed projects

Dynamic viscosity of binary and ternary mixtures containing poly(ethylene glycol), potassium phosphate, and water

Dynamic viscosity of binary mixtures of poly(ethylene glycol) molar mass 1500 da + water, potassium phosphate + water, and ternary mixtures of poly(ethylene glycol) molar mass 1500 da + potassium phosphate + water were determined at 303.15 K Binary and ternary mixture viscosities showed a direct logarithm-type relation with the increase of poly(ethylene glycol) and potassium phosphate contents. The models used for viscosity correlation gave a good fit to the experimental data.

Kinetics and product distribution of p-nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p-nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright (C) 2011 John Wiley & Sons, Ltd.

Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Densities and refractive indices for the ternary mixture methanol/propan-1-Ol/acetonitrile

Refractive indices, n(D), and densities, rho, at 298.15 K were measured for the ternary mixture methanol (MeOH)/propan-1-ol (1-PrOH)/acetonitrile (MeCN) for a total of 22 mole fractions, along with 18 mole fractions of each of the corresponding binary mixtures, methanol/propan-1-ol, propan-1-ol/acetonitrile and methanol/acetonitrile. The variation of excess refractive indices and excess molar volumes with composition was modeled by the Redlich-Kister polynomial function in the case of binary mixtures and by the Cibulka equation for the ternary mixture. A thermodynamic approach to excess refractive indices, recently proposed by other authors, was applied for the first time to ternary liquid mixtures. Structural effects were identified and interpreted both in the binary and ternary systems. A complex relationship between excess refractive indices and excess molar volumes was identified, revealing all four possible sign combinations between these two properties. Structuring of the mixtures was also discussed on the basis of partial molar volumes of the binary and ternary mixtures.

Optimization of solvent mixtures for extraction from bark of Schinus terebinthifolius by a statistical mixture-design technique and development of a UV-Vis spectrophotometric method for analysis of total polyphenols in the extract

A statistical mixture-design technique was used to study the effects of different solvents and their mixtures on the yield, total polyphenol content, and antioxidant capacity of the crude extracts from the bark of Schinus terebinthifolius Raddi (Anacardiaceae). The experimental results and their response-surface models showed that ternary mixtures with equal portions of all the three solvents (water, ethanol and acetone) were better than the binary mixtures in generating crude extracts with the highest yield (22.04 ± 0.48%), total polyphenol content (29.39 ± 0.39%), and antioxidant capacity (6.38 ± 0.21). An analytical method was developed and validated for the determination of total polyphenols in the extracts. Optimal conditions for the various parameters in this analytical method, namely, the time for the chromophoric reaction to stabilize, wavelength of the absorption maxima to be monitored, the reference standard and the concentration of sodium carbonate were determined to be 5 min, 780 nm, pyrogallol, and 14.06% w v-1, respectively. UV-Vis spectrophotometric monitoring of the reaction under these conditions proved the method to be linear, specific, precise, accurate, reproducible, robust, and easy to perform.

Microencapsulation of turmeric oleoresin in binary and ternary blends of gum arabic, maltodextrin and modified starch

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optimization of Pothomorphe umbellata (L.) Miquel topical formulations using experimental design

Pothomorphe umbellata is a native plant widely employed in the Brazilian popular medicine. This plant has been shown to exert a potent antioxidant activity on the skin and to delay the onset and reduce the incidence of UVB-induced skin damage and photoaging. The aim of this work was to optimize the appearance, the centrifuge stability and the permeation of emulsions containing R umbellata (0. 1% 4-nerolidylchatecol). Experimental design was used to study ternary mixtures models with constraints and graphical representation by phase diagrams. The constraints reduce the possible experimental domain, and for this reason, this methodology offers the maximum information while requiring the minimum investment. The results showed that the appearance follows a linear model, and that the aqueous phase was the principal factor affecting the appearance; the centrifuge stability parameter followed a mathernatic quadratic model and the interactions between factors produced the most stable emulsions; skin permeation was improved by the oil phase, following a linear model generated by data analysis. We propose as optimized P. umbellata formulation: 68.4% aqueous phase, 26.6% oil phase and 5.0% of self-emulsifying phase. This formulation displayed an acceptable compromise between factors and responses investigated. (c) 2007 Elsevier B.V. All rights reserved.

Fresh-state properties of self-compacting mortar and concrete with combined use of limestone filler and fly ash

This paper presents the results of a study on the behaviour of self-compacting concrete (SCC) in the fresh and hardened states, produced with binary and ternary mixes of fly ash (FA) and limestone filler (LF), using the method proposed by Nepomuceno. His method determines the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) easily and efficiently, whilst guaranteeing the SCC properties in both the fresh and hardened states. For this, 11 SCMs were studied: one with cement (C) only; three with FA at 30%, 60% and 70% C substitution; three with LF at 30%, 60% and 70% C substitution; four with FA + LF in combinations of 10-20%, 20-10%, 20-40% and 40-20% C substitution. Once the composition of these mortars was defined, 18 SCC mixes were produced: 14 binary SCC mixes were produced with the seven binary mortar mixes, and four ternary SCC mixes were produced with the four ternary mortar mixes. In addition to the methodology proposed by Nepomuceno, the combined use of FA and LF in ternary mixtures was tested. The results confirmed that the method could yield SCC with adequate properties in both the fresh and hardened states. It was also possible to determine the SCC composition parameters in the mortar phase (self-compacting mortar - SCM) that will guarantee the SCC properties in both the fresh and hardened states, as confirmed through the optimized behaviour of the SCC in the fresh state and the promising results in the hardened state (compressive strength). The potential demonstrated by the joint use of LF and FA through the synergetic interaction of both additions is emphasized.

Materials and Mix Optimization Procedures for PCC Pavements, March 2006

Severe environmental conditions, coupled with the routine use of deicing chemicals and increasing traffic volume, tend to place extreme demands on portland cement concrete (PCC) pavements. In most instances, engineers have been able to specify and build PCC pavements that met these challenges. However, there have also been reports of premature deterioration that could not be specifically attributed to a single cause. Modern concrete mixtures have evolved to become very complex chemical systems. The complexity can be attributed to both the number of ingredients used in any given mixture and the various types and sources of the ingredients supplied to any given project. Local environmental conditions can also influence the outcome of paving projects. This research project investigated important variables that impact the homogeneity and rheology of concrete mixtures. The project consisted of a field study and a laboratory study. The field study collected information from six different projects in Iowa. The information that was collected during the field study documented cementitious material properties, plastic concrete properties, and hardened concrete properties. The laboratory study was used to develop baseline mixture variability information for the field study. It also investigated plastic concrete properties using various new devices to evaluate rheology and mixing efficiency. In addition, the lab study evaluated a strategy for the optimization of mortar and concrete mixtures containing supplementary cementitious materials. The results of the field studies indicated that the quality management concrete (QMC) mixtures being placed in the state generally exhibited good uniformity and good to excellent workability. Hardened concrete properties (compressive strength and hardened air content) were also satisfactory. The uniformity of the raw cementitious materials that were used on the projects could not be monitored as closely as was desired by the investigators; however, the information that was gathered indicated that the bulk chemical composition of most materials streams was reasonably uniform. Specific minerals phases in the cementitious materials were less uniform than the bulk chemical composition. The results of the laboratory study indicated that ternary mixtures show significant promise for improving the performance of concrete mixtures. The lab study also verified the results from prior projects that have indicated that bassanite is typically the major sulfate phase that is present in Iowa cements. This causes the cements to exhibit premature stiffening problems (false set) in laboratory testing. Fly ash helps to reduce the impact of premature stiffening because it behaves like a low-range water reducer in most instances. The premature stiffening problem can also be alleviated by increasing the water–cement ratio of the mixture and providing a remix cycle for the mixture.

Quimiometria I: calibração multivariada, um tutorial

The aim of this work is to present a tutorial on Multivariate Calibration, a tool which is nowadays necessary in basically most laboratories but very often misused. The basic concepts of preprocessing, principal component analysis (PCA), principal component regression (PCR) and partial least squares (PLS) are given. The two basic steps on any calibration procedure: model building and validation are fully discussed. The concepts of cross validation (to determine the number of factors to be used in the model), leverage and studentized residuals (to detect outliers) for the validation step are given. The whole calibration procedure is illustrated using spectra recorded for ternary mixtures of 2,4,6 trinitrophenolate, 2,4 dinitrophenolate and 2,5 dinitrophenolate followed by the concentration prediction of these three chemical species during a diffusion experiment through a hydrophobic liquid membrane. MATLAB software is used for numerical calculations. Most of the commands for the analysis are provided in order to allow a non-specialist to follow step by step the analysis.

Lipídios estruturados obtidos a partir da mistura de gordura de frango, sua estearina e triacilgliceróis de cadeia média: I- Composição em ácidos graxos e em triacilgliceróis

The purpose of this study is to analyze the interactions that occur in binary and ternary fat blends between medium and long chain triacylglycerols and their structured lipids obtained by chemical interesterification through the analysis of their physico-chemical properties. The synthesized structured triacylglycerols presented from 14.8 to 58.4% medium chain fatty acids, from 15.7 to 37.2% saturated fatty acids, from 19.2 to 47.5% monounsaturated fatty acids, and from 6.7 to 15.2% essential fatty acids. Chemical interesterification modified the behavior of binary and ternary mixtures and new types of triacylglycerol groups were formed.