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- Deep Eutectic Solvents (DES) based on sulphur for silicon surfaces as alternative lubricantsPublication . Antunes, Mónica; Martins, Anne-Sophie; Freire, Mariana de Sá; Caetano, Fernando J. P.; Diogo, Herminio; Colaco, Rogério; Branco, Luís C.; Saramago, BenildeDeep eutectic mixtures composed of hydrogen-bond donors and hydrogen-bond acceptors, the so-called DESs, have recently being proposed as possible “green” alternatives to mineral oils and ionic liquids (ILs) in the lubrication of steel surfaces. DESs have similar physical properties to ILs but have the advantage of being cheaper and easier to prepare. In this work, new DESs containing sulphur units in their structure were prepared and tested in the lubrication of silicon surfaces which are relevant for nano/microelectromechanical systems (NEMS/MEMS). The following new DESs were prepared: dibutil-ethyl sulfonium ethylsulfate: polyethylene glycol ([S4,4,2][EtSO4]:PEG), ethyl-tetrahydrothiophenium ethylsulfate: polyethylene glycol ([C2-THT][EtSO4]:PEG, cis-1-ethyl-3methylimidazolium canforsulfonate: polyethylene glycol ([C2MIM][(S)-CSA]:PEG), and 1,3-dimethylpiridinium methyl sulfate: polyethylene glycol ([C1-3-pic][MeSO4]:PEG). Other DES, already known, were tested for comparison purposes: tetrabutylammonium bromide: tetrahydrothiophene 1,1-dioxide ([N4,4,4,4][Br]:Sulfolane), choline chloride: polyethylene glycol (ChCl:PEG), and tetrabutylammonium bromide: polyethylene glycol ([N4,4,4,4][Br]:PEG). All DESs were characterized in terms of their water content, viscosity, wettability, and tribological properties. The friction coefficients were measured in a nanotribometer using steel spheres against Si surfaces. The new DES prepared from ILs based on the sulfur-containing anions showed good tribological performance, but the best results were obtained with [C2MIM][(S)-CSA]:PEG and [C1-3-pic][MeSO4]:PEG which reduced the friction coefficients to values < 0.1, typical of excellent lubrication conditions.
- 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
- 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.
- Revisiting odd-even effects in n-alkane systemsPublication . Fausto, Rui; Sequeira, Maria Carolina; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Nikitin, Timur; Fausto, Ruin-Alkanes have been widely studied for different applications. Recently, they became still more popular due to their exceptional characteristics as phase change materials (PCMs) for thermal energy storage (TES) applications [1]. In our research group, during the last three years, we have been studying the phase equilibrium behaviour of some binary systems with potential application as PCMs, including n-alkanes [2,3]. In this study, the n-alkanes family has shown some intriguing effects, related to the odd or even number of carbon atoms of the molecules on the characteristics of their solid-liquid phase equilibria. Several studies regarding the solid phase properties have been carried out to understand this type of phenomena in n-alkanes and compounds whose molecules contain alkyl groups. It has been established that n-alkanes exhibit different crystal packing arrangements according to their odd or even number of carbon atoms in their chains [4]. As a result, several properties are seen to be affected by the number of carbon atoms, revealing remarkable odd-even effects, which can eventually be used as an advantage for some specific applications [5]. This is particularly important to interpret and predict the solid-liquid phase equilibrium types of the diagrams, which is a key issue to select PCMs for TES applications. Most of the studies involving the properties of n-alkanes are devoted to the liquid phase. Therefore, along the years, a wide range of properties have been measured, predicted, correlated, and interpreted, including viscosity, density, heat capacity, vapour pressure, flash point, boiling point, and thermal conductivity. It is generally known that linear alkanes are an interesting homologous series, because they show a considerable regularity in their fluid phase properties, which allows to establish, for example, simple correlations based on the number of carbon atoms in the molecular chain [4]. Because of the raising importance of energy storage, namely TES, and the application of alkanes as PCMs, interest in their solid-liquid phase equilibria has increased. Consequently, it is interesting to picture an overall image on the thermophysical properties of n-alkanes, and, in particular to study the predictability of the main characteristics of their solid-liquid phase equilibria. Thus, this work aims to be a comprehensive view on the thermophysical properties and phase equilibrium behaviour of n-alkanes and their relation to the odd or even carbon atoms present in the alkyl chain.
- Seeking new low temperature energy storage systems: n-alkanes as phase change materialsPublication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Nikitin, Timur; Caetano, Fernando J. P.; Fareleira, João M. N. A.; Fausto , Rui; Diogo, HerminioOver the last decades, the increasing need for energy has been a tremendous challenge. Until now, fossil fuels have been the dominant energy source, however, due to their environmental consequences, renewable energies are the promising solution for the future.1 Nevertheless, the intermittent nature of most renewable energy sources often leads to a discrepancy between the energy produced and its consumption, which highlights the crucial role of energy storage technologies in enhancing clean energy utilization.2 From all energy storage solutions, thermal energy storage (TES) is one of the most promising options, showing substantial energy storage capacity at an acceptable cost.3 For these applications, phase change materials (PCMs) are particularly important, especially for low temperature energy storage systems. Linear alkanes (n-alkanes) have been studied as good candidates for TES applications mainly due to their singular phase transition performance, among others.4 In the present work, it has also been studied the differences due to the odd-even carbon chain number on the solid-liquid equilibrium properties that these materials can present, which is a key aspect crucial to characterize the systems for an upcoming use as PCMs. 4,5 to be used as new PCMs For TES applications, solid-liquid phase equilibrium is determinant to characterize the phase transitions which are more important for the application of these systems, as new PCMs. As an example, in the logistics associated to the transport of perishable consumables, like vaccines and other pharmaceutical products, TES plays an important role. In the present context, this work aims at the characterization of some selected n-alkane binary systems that can be used for energy storage applications at low temperatures, including the construction of the solid-liquid binary phase diagrams at sub-zero temperatures using differential scanning calorimetry (DSC), hot stage microscopy (HSM) and Raman spectroscopy. The studied systems composed by odd and even n-alkanes, have showed different solid-liquid equilibrium behaviour. The HSM and Raman spectroscopy were fundamental to obtain the binary phase diagrams, but also to visualize the changes taking place in real time as a function of temperature and often the identification of the different solid and liquid phases exhibited by these systems. This work presents some preliminary phase equilibrium data, which, to the knowledge of the authors, are not available in the literature, and are presently being prepared for publication in an international scientific journal. The presentation will also include comparisons with spread literature data, when available. All these studied systems have promising characteristics for low temperature energy storage. With this work, it is also demonstrated how solid-liquid phase equilibrium studies are a central key to select the most adequate phase change material for a specific TES application.
- Low temperature thermal energy storage: insights into odd-even n-alkane systemPublication . Sequeira, Maria Carolina; Nogueira, Bernardo; Nikitin, Timur; Caetano, Fernando J. P.; Diogo, Herminio; Fausto, Rui; Fareleira, João M. N. A.
- Solid-liquid phase equilibrium: in search of suitable PCMs for low temperature energy storagePublication . Sequeira, Maria Carolina; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.
- On capillary viscosity measurements: how far do surface tension effects go?Publication . Sequeira, Maria Carolina; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Santos, Fernando J. V.; Serro, A. P.Viscosity is a fundamental thermophysical property of liquids making it very important particularly in the industry. Capillary viscometers have been widely used for viscosity measurements in different applications, the most relevant being the definition of viscosity standards, traceable to the primary water viscosity standard, by metrological institutions and industrial applications, mostly for quality control. Practical viscometry is based on the internationally accepted primary standard value for the kinematic viscosity of water at 20ºC and atmospheric pressure, which has been measured using capillary viscometers [1]. However, due to the water surface tension, viscosity measurements which have been related to water as a primary standard, can be significantly affected. It is difficult to rigorously assess the surface tension effects on capillary viscometers, and the practical way to avoid this problem is to use long capillaries, which are not appropriate for routine measurements [1-3]. After several experimental studies, using different types of viscometers, the usual procedure to correct surface tension effects in capillary viscosity measurements adopted by different authors, is to employ an empirical expression [1-4]. Additionally, other types of problems exist as the need to perform a kinetic energy correction which must also be taken into consideration [1]. The main goal of this work was to perform the calibration of a suspended-level, or Ubbelohde, capillary viscometer, which is not a long capillary viscometer, as well as the study of corrections to be used for the measurements performed with it. The experimental work covers the calibration of that Ubbelohde capillary viscometer, the evaluation of the uncertainty of the corresponding viscometer constant and the overall uncertainty of the measurements performed with it. This study includes the evaluation of the necessary corrections for kinetic energy and surface tension effects and, finally, the analysis of the case of a set of measurements performed with n-tetradecane. The ultimate purpose of this work is to obtain the lowest uncertainty for the Ubbelohde capillary viscometer 541 01/Ia, and to understand the need for the corrections that must be considered when using capillary viscometers and how they should be applied.