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- Viscosity measurements of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM OTf) at high pressures using the vibrating wire techniquePublication . Sequeira, Maria Carolina; Avelino, Helena Maria da Nóbrega Teixeira; Caetano, Fernando J. P.; Fareleira, João M. N. A.The goal of the present work is to contribute to the characterization of ionic liquids by measuring their viscosity at high pressures. As 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM OTf) has been used as a solvent in CO2 capture processes, the temperature and pressure ranges of the measurements cover the intervals used in those processes. Measurements of the viscosity of EMIM OTf along five isotherms in the range (298–358) K and at pressures up to 50 MPa, have been performed using the vibrating wire technique in the forced mode of operation. As far as the authors are aware, these are the first measurements of this ionic liquid at pressures higher than 0.1 MPa, to be published. The viscosity results were correlated with the molar volume, using a modified hard-spheres model. The root mean square (σ) deviation of the data from the correlation is less than 0.5% The expanded uncertainty of the present viscosity data is estimated as ±2.0% at a 95% confidence level. As a complement, the pressure-viscosity coefficient has been calculated within the temperature range of the present results. Previous studies of the influence of the electric conductivity of ionic liquids, including EMIM OTf, in the vibrating wire method, have been taken into account for the present work. Complementary measurements of the density have been performed along seven isotherms in the temperature range from (298–363) K and pressures from (0.1–70) MPa. The density measurements were carried out with an Anton Paar vibrating U-tube densimeter and the raw data were corrected for viscosity effects. The density results were correlated with the temperature and pressure using a modified Tait equation. The expanded uncertainty of the present density data is estimated as ±0.2% at a 95% confidence level.
- Viscosity and density of two 1-alkyl-3-methyl-imidazolium triflate ionic liquids at high pressures: experimental measurements and the effect of alkyl chain lengthPublication . Sequeira, Maria Carolina; Avelino, Helena Maria da Nóbrega Teixeira; Caetano, Fernando J. P.; Fareleira, João M. N. A.New measurements of the viscosity of 1-butyl-3-methyl-imidazolium triflate ([BMIM][OTf]) and 1-hexyl-3-methyl-imidazolium triflate ([HMIM][OTf]) have been carried out at high pressures, using a vibrating-wire technique operated in the forced mode of oscillation. The measurements for [BMIM][OTf] have been performed along six isotherms from 298 to 358 K at pressures up to 50 MPa. The viscosity measurements for [HMIM][OTf] have been carried out along five isotherms from 303 to 358 K at pressures up to 50 MPa. The estimated uncertainty of the measurements is less than U(η) = 0.02·η for viscosities up to 68 mPa·s and less than U(η) = 0.026·η for higher viscosities, with a confidence level of 0.95 (k = 2). For both ionic liquids, complementary density measurements have been performed using an Anton Paar HP densimeter in the same temperature and pressure ranges as those used for the viscosity measurements. The density results have an uncertainty smaller than U(ρ) = 0.002·ρ with a confidence level of 0.95 (k = 2). The viscosity results were correlated with the density data using a previously described hard-sphere-based technique. The individual correlations are able to describe the viscosity results for each liquid with an uncertainty smaller than the estimated uncertainty of the experimental data. The effect of alkyl substituents on the viscosity and the density of these ionic liquids has been analyzed. For this purpose, previously published results for the viscosity and density of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]) have been considered in addition to the data obtained in the present work for [BMIM][OTf] and [HMIM][OTf].
- Viscosity and density measurements of Poly(ethyleneglycol) 200 and Poly(ethyleneglycol) 600 at high pressuresPublication . Sequeira, Maria Carolina; Avelino, Helena Maria da Nóbrega Teixeira; Caetano, Fernando J. P.; Fareleira, João M. N. A.New measurements for the viscosity and density of poly(ethyleneglycol) 200 [PEG 200] and of poly(ethyleneglycol) 600 [PEG 600], at pressures up to 50 MPa, are presented. The temperature range of the measurements performed for PEG 200 was from 293 to 348 K and for PEG 600 was from 303 to 348 K. A vibrating wire viscometer operated in the steady-state mode was used to carry out the measurements with an estimated overall uncertainty less than U(η) = 0.02·η, for viscosities up to 68 mPa s, and less than U(η) = 0.026·η, for higher viscosities with a confidence level of 0.95 (k = 2). Complementary density measurements for both PEGs were performed in the same ranges of temperature and pressure as for the viscosity measurements, using an Anton Paar HP vibrating tube densimeter, with an estimated overall uncertainty of about U(ρ) = 0.002·ρ with a confidence level of 0.95 (k = 2). Moreover, pressure–viscosity coefficients were obtained for both PEGs. A method based on a dense hard-sphere fluid theory was used to correlate the viscosity data with the density, for both PEGs, with a deviation of the experimental results less than 1%. A modified Tait equation was used to correlate the density results with temperature and pressure.
- Viscosity and density measurements on liquid n-heptadecane at high pressuresPublication . Sequeira, Maria Carolina; Avelino, Helena Maria da Nóbrega Teixeira; Caetano, Fernando J. P.; Fareleira, João M. N. A.This article reports novel measurements of the viscosity, η, of liquid n-heptadecane at pressures up to 70 MPa, along six isotherms between 303 and 358 K. The experiments were carried out using a vibrating wire viscometer operated in the forced mode. The 303 and 313 K isotherms have a restricted range of pressures to avoid eventual solidification. The present measurements have an uncertainty less than U(η) = 0.015·η with a confidence level of 0.95. Complementary measurements of the density, ρ, were performed with the same ranges of temperature and pressure, using a DMA HP Anton Paar U-tube densimeter, with a DMA 5000 instrument as a reading unit. The overall maximum uncertainty is U(ρ) = 0.002·ρ with a confidence level of 0.95. The article provides a correlation of the viscosity of compressed liquid n-heptadecane with the molar volume, constructed by means of a scheme based on a modified hard-sphere theory, which describes the experimental data within ca. 1%. A program is provided in the Supporting Information to promptly perform interpolation of the viscosity as a function of temperature and pressure. The isothermal compressibility and the isobaric thermal expansivity were calculated from the density. Viscosity–pressure coefficients have also been determined from the viscosity.
- Di-Alkyl adipates as new phase change material for low temperature energy storagePublication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, RuiThis work is a contribution to the thermal characterization of a selected binary system of two di-n-alkyl adipates that can be used as phase change material for thermal energy storage at low temperatures. The construction of the solid–liquid phase diagram using differential scanning calorimetry (DSC), complemented with Raman Spectroscopy studies for the system composed by diethyl and dibutyl adipates is presented. The solidus and liquidus equilibrium temperatures were determined by DSC for the pure components and 30 binary mixtures at selected molar compositions were used to construct the corresponding solid–liquid phase diagram. The binary system of diethyl and dibutyl adipates presents eutectic behaviour at low temperatures. The eutectic temperature was found at 240.46 K, and the eutectic composition was determined to occur at the molar fraction xdibutyl = 0.46. Additionally, the system shows a polymorphic transition, characteristic of dibutyl adipate, occurring at ca. 238 K, confirmed by optical microscopy. To the best of our knowledge, no reference to the phase diagram of the present system could be found in the literature. Raman spectroscopy was essential to complement the construction of the phase equilibrium diagram, enabling the identification of the solid and liquid phases of the system. Finally, the liquidus curve of the phase diagram was also successfully predicted using a suitable fitting equation, being the root mean square deviation of the data from the correlation equal to 0.54 K. In addition, this fitting operation enabled a correct prediction of the eutectic composition of the system.
- Adipates as new phase change material: seeking for a low temperature energy storage systemPublication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, RuiThe recent and endless increasing need for energy is requiring imperative and efficient solutions. Renewable energies are an effective solution, but they are also intermittent, which often leads to a gap between the availability of energy and its demand. Therefore, energy storage becomes crucial for improving the efficiency by reducing the mismatch between demand and supply thus offering better management capabilities. The use of phase change materials (PCMs) became an attractive technology, especially for active cooling systems. In particular, eutectic systems can be designed for each application, allowing significant energy savings, which is very relevant in what concerns economic and environmental sustainability [1]. Equilibrium studies and their phase diagrams are crucial to characterize the behavior of these systems, particularly for new PCMs [2]. This work aims the characterization of a selected type of binary system composed by di-n-alkyl adipates that can be used for energy storage at low temperatures, starting by the construction of solid-liquid phase diagram based on Differential Scanning Calorimetry (DSC) and Raman Spectroscopy results. The studied system is a binary mixture of diethyl and dibutyl adipates and reveals to behave as a eutectic system at low temperatures, possessing also polymorphism, therefore presenting a relatively complex phase diagram. The eutectic point was found around -33ºC and the polymorphism transition, being characteristic of the dibutyl adipate, occurs at around -36ºC for the overall phase diagram. Raman spectroscopy was fundamental concerning the construction of the phase diagram, enabling to identify the different solid and liquid phases of the system. This work provides new phase equilibrium data, which, to the knowledge of the authors, are the first in the literature, concerning these compounds. The studied binary system has promising characteristics for low temperature energy storage. It is also demonstrated how solid-liquid-phase equilibrium studies are the key to select the most appropriate phase change material for a specific thermal energy storage (TES) application.
- Low temperature energy storage PCM systems: phase equilibrium studiesPublication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, Rui
- Viscosity measurements of poly(ethyleneglycol) 400 [PEG 400] at temperatures from 293 K to 348 K and at pressures up to 50 MPa using the vibrating wire techniquePublication . Sequeira, Maria Carolina; Pereira, Marta F. V.; Avelino, Helena Maria da Nóbrega Teixeira; Caetano, Fernando J. P.; Fareleira, João M. N. A.The article reports new measurements of the viscosity of Poly(ethyleneglycol) 400 [PEG 400] in the range (293–348) K and pressures up to 50 MPa. Complementary measurements of the density of the same sample of PEG 400 have been made covering the ranges of temperature and pressure, (293–353) K and (0.1–50) MPa, respectively. The viscosity measurements were performed using the vibrating wire technique in the forced mode of oscillation and the density measurements were carried out with an Anton Paar vibrating U-tube densimeter. The density raw data were corrected for viscosity effects. The overall uncertainty of the viscosity measurements is estimated to be less than ±2% for viscosities up to 68 mPa s and less than ±2.6% for higher viscosities. The densities have an estimated overall uncertainty of ±0.2%. The rheological behaviour of Poly(ethylene Glycol) 400 has also been studied, using a cone-plate Brookfield viscometer, in a temperature range between (293 and 333) K. The measurements were carried out at shear rates up to 20 s−1 and shear stresses up to 2.20 Pa and have evidenced Newtonian behaviour. The viscosity data obtained were correlated by means of a modified hard-sphere based correlation technique. The relative root mean square, rms, deviation of the experimental results from the correlation equations is 0.54%, and their bias is practically zero. The density data obtained were correlated using a Tait-type equation. As a complement of the present study, the surface tension of PEG 400 was measured by the pendant drop method. This study aims to be useful for viscosity measurements using capillary viscometers. As far as the authors are aware, the present viscosity measurements are the first results to be published for PEG 400 at pressures higher than atmospheric pressure.
- Solid–liquid phase equilibrium of the n-Nonane + n-Undecane system for low-temperature thermal energy storagePublication . Nikitin, Timur; Sequeira, Maria Carolina; Caetano, Fernando J. P.; Fareleira, João M. N. A.; Fausto , Rui; Diogo, HerminioThe current article presents an exploration of the solid–liquid phase diagram for a binary system comprising n-alkanes with an odd number of carbon atoms, specifically n-nonane (n-C9) and n-undecane (n-C11). This binary system exhibits promising characteristics for application as a phase change material (PCM) in low-temperature thermal energy storage (TES), due to the fusion temperatures of the individual components, thereby motivating an in-depth investigation of the solid–liquid phase diagram of their mixtures. The n-nonane (n-C9) + n-undecane (n-C11) solid–liquid phase equilibrium study herein reported includes the construction of the phase diagram using Differential Scanning Calorimetry (DSC) data, complemented with Hot–Stage Microscopy (HSM) and low-temperature Raman Spectroscopy results. From the DSC analysis, both the temperature and the enthalpy of solid–solid and solid–liquid transitions were obtained. The binary system n-C9 + n-C11 has evidenced a congruent melting solid solution at low temperatures. In particular, the blend with a molar composition xundecane = 0.10 shows to be a congruent melting solid solution with a melting point at 215.84 K and an enthalpy of fusion of 13.6 kJ·mol–1. For this reason, this system has confirmed the initial signs to be a candidate with good potential to be applied as a PCM in low-temperature TES applications. This work aims not only to contribute to gather information on the solid–liquid phase equilibrium on the system n-C9 + n-C11, which presently are not available in the literature, but especially to obtain essential and practical information on the possibility to use this system as PCM at low temperatures. The solid–liquid phase diagram of the system n-C9 + n-C11 is being published for the first time, as far as the authors are aware.
- Capillary viscometry for routine measurements of newtonian liquidsPublication . Sequeira, Maria Carolina; Caetano, Fernando J. P.; Fareleira, João M. N. A.Viscosity is a thermophysical property of paramount importance, being essential for many scientific and industrial applications. The most common instruments for its measurement are glass capillary viscometers. Therefore, the use of capillary viscometers is widespread both in industry and in research. The range of viscosities of interest range from lower than that of water to several orders of magnitude higher values, the measurement of which requires different capillary viscometers. Most of the practical applications concern routine instruments, mainly for quality control. One main issue for the utilization of capillary viscometers relates to the need for their calibration, assuring its traceability to the water primary viscosity standard, to certify its worldwide validity. The present paper focuses on capillary instruments dedicated to perform viscosity measurements on Newtonian organic liquids at atmospheric pressure, as it is assumed that is the most widespread type of application for these viscometers. Capillary viscometry has a completely well-defined working equation, namely, the Hagen–Poiseuille equation. However, the practical performance of the measuring instruments deviates from that working equation. Most of those deviations are currently considered by many users. However, some of those deviations have not reached that status yet, like those concerning the effects due to the surface tension of the sample on the measurements. All these aspects are summarized and analyzed in the present article, together with a brief general description of the most common types of capillary viscometers, namely, the Ostwald and the constant-level or Ubbelohde instruments.