Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C₁OC_n][Sal]) with n = 3–11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

Thermal Properties of Alkyl-triethylammonium bis{(trifluoromethyl)sulfonyl}imide Ionic Liquids

In this work, we address the thermal properties of selected members of a
homologous series of alkyltriethylammonium bisf(trifluoromethyl)sulfonylgimide ionic
liquids. Their phase and glass transition behavior, as well as their standard isobaric heat
capacities at 298.15 K, were studied using differential scanning calorimetry (DSC),
whereas their decomposition temperature was determined by thermal gravimetry analysis.
DSC was further used to measure standard molar heat capacities of the studied ionic liquids
and standard molar heat capacity as a function of temperature for hexyltriethylammonium,
octyltriethylammonium, and dodecyltriethylammonium bisf(trifluoromethyl)sulfonylgimide
ionic liquids. Based on the data obtained, we discuss the influence of the alkyl chain
length of the cation on the studied ionic liquids on the measured properties. Using viscosity
data obtained in a previous work, the liquid fragility of the ionic liquids is then discussed.
Viscosity data were correlated by the VTF equation using a robust regression along a
gnostic influence function. In this way, more reliable VTF model parameters were obtained than in our previous work and a good estimate of the liquid fragility of the ionic liquids was made.

Effect of poly ethylene glycol on the mechanical and thermal properties of bioactive Poly (ε–caprolactone) melt extrudates for pharmaceutical applications

This paper investigates the effects of polyethylene glycol (PEG), on the mechanical and thermal properties of nalidixic acid/ploy ε-caprolactone (NA)/PCL blends prepared by hot melt extrusion. The blends were characterized by tensile and flexural analysis, dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. Experimental data indicated that the addition of NA caused loss of the tensile strength and toughness of PCL. Thermal analysis of the PCL showed that on addition of the thermally unstable NA, thermal degradation occurred early and was autocatalytic. However, the NA did benefit from the heat shielding provided by the PCL matrix resulting in more thermally stable NA particles. Results show that loading PEG in the PCL had a detrimental effect on the tensile strength and toughness of the blends, reducing them by 20-40%. The partial miscibility of the PCL-PEG system, causes an increase in Tg. While increases in the crystallinity is attributed to the plasticisation effect of PEG and the nucleation effect of NA. The average crystal size increased by 8% upon PEG addition.

Optimization and Prediction of Mechanical and Thermal Properties of Graphene/LLDPE Nanocomposites by Using Artificial Neural Networks

The focus of this work is to develop the knowledge of prediction of the physical and chemical properties of processed linear low density polyethylene (LLDPE)/graphene nanoplatelets composites. Composites made from LLDPE reinforced with 1, 2, 4, 6, 8, and 10 wt% grade C graphene nanoplatelets (C-GNP) were processed in a twin screw extruder with three different screw speeds and feeder speeds (50, 100, and 150 rpm). These applied conditions are used to optimize the following properties: thermal conductivity, crystallization temperature, degradation temperature, and tensile strength while prediction of these properties was done through artificial neural network (ANN). The three first properties increased with increase in both screw speed and C-GNP content. The tensile strength reached a maximum value at 4 wt% C-GNP and a speed of 150 rpm as this represented the optimum condition for the stress transfer through the amorphous chains of the matrix to the C-GNP. ANN can be confidently used as a tool to predict the above material properties before investing in development programs and actual manufacturing, thus significantly saving money, time, and effort.

Experimental investigation of thermal inertia properties in hemp-lime concrete walls

Hemp-lime concrete is a sustainable alternative to standard building wall materials, with low associated embodied energy. It exhibits good hygric, acoustic and thermal properties, making it an exciting, sustainable building envelope material. When cast in temporary shuttering around a timber frame, it exhibits lower thermal conductivity than concrete, and consequently achieves low U-values in a primarily mono-material wall construction. Although cast relatively thick hemp-lime walls do not generally achieve the low U-values stipulated in building regulations. However assessment of its thermal performance through evaluation of its resistance to thermal transfer alone, underestimates its true thermal quality. The thermal inertia, or reluctance of the wall to change its temperature when exposed to changing environmental temperatures, also has a significant impact on the thermal quality of the wall, the thermal comfort of the interior space and energy consumption due to space heating. With a focus on energy reduction in buildings, regulations emphasise thermal resistance to heat transfer with only less focus on thermal inertia or storage benefits due to thermal mass. This paper investigates dynamic thermal responsiveness in hemp-lime concrete walls. It reports the influence of thermal conductivity, density and specific heat through analysis of steady state and transient heat transfer, in the walls. A novel hot-box design which isolates the conductive heat flow is used, and compared with tests in standard hot-boxes. Thermal diffusivity and effusivity are evaluated, using experimentally measured conductivity, based on analytical relationships. Experimental results evident that hemp-lime exhibits high thermal inertia. They show the thermal inertia characteristics compensate for any limitations in the thermal resistance of the construction material. When viewed together the thermal resistance and mass characteristics of hemp-lime are appropriate to maintain comfortable thermal indoor conditions and low energy operation.

Effect of MWCNT addition on the thermal and rheological properties of polymethyl methacrylate bone cement

Multi-walled carbon nanotube (MWCNT)/polymethyl methacrylate (PMMA) composites with loadings ranging from 0.1 to 1.0 wt.% were prepared for use as bone cement. Unfunctionalised, carboxyl and amine functionalised MWCNT were used. Thermal properties were characterised in accordance with the International Standard for acrylic cements, ISO 5833:2002. The rate of reaction exotherm generated and thermal necrosis index (TNI) values were calculated. Polymerisation kinetics were characterised using parallel plate rheology and the exotherm during polymerisation was reduced by ˜4–34%, as a consequence of the MWCNT thermal conductivity. The rate of reaction was significantly altered, such that the setting times of the cements were extended (˜3–24%). Consequently, significant decreases in TNI values (ranging from 3% to 99%) were recorded, which could reduce the exothermic temperatures experienced in vivo and therefore prevent the likelihood of polymerising PMMA cement causing thermally-induced bone tissue necrosis. Thermal data was supported by the rheological characterisation results. Onset of polymerisation for PMMA cement exhibited a strong linear increase as a function of MWCNT loading, however, polymer gelation was not affected to the same degree. It is proposed that the chemically functionalised MWCNT altered PMMA bone cement polymerisation kinetics, reducing the rate of polymerisation, and hence, the reaction exotherm.

Hygrothermal Features of Laterite Dimension Stones for Sub-Saharan Residential Building Construction

The building sector is widely recognized as having a major impact on sustainable development. Both in developed and developing countries, sustainability in buildings approaches are growing. Laterite dimension stone (LDS) is a building material that was traditionally used in sub-Saharan Africa, but its technical features still need to be assessed. This article presents some results of a study focused on the characterization of LDS exploited in Burkina Faso for building purposes. The measured average thermal conductivity is 0.51  W/mK, which increases with water content and evolves with the specific gravity and with porosity. Rock mineral phases (quartz, goethite, hematite, magnetite) are cemented by kaolinite. The porosity of the material is high (30%), with macropores visible on the surface and found in the rock inner structure as well. Results from the hygrothermal monitoring of a pilot building are also presented.

Thermal conductivity measurement of liquids in a microfluidic device

A new microfluidic-based approach to measuring liquid thermal conductivity is developed to address the requirement in many practical applications for measurements using small (microlitre) sample size and integration into a compact device. The approach also gives the possibility of high-throughput testing. A resistance heater and temperature sensor are incorporated into a glass microfluidic chip to allow transmission and detection of a planar thermal wave crossing a thin layer of the sample. The device is designed so that heat transfer is locally one-dimensional during a short initial time period. This allows the detected temperature transient to be separated into two distinct components: a short-time, purely one-dimensional part from which sample thermal conductivity can be determined and a remaining long-time part containing the effects of three-dimensionality and of the finite size of surrounding thermal reservoirs. Identification of the one-dimensional component yields a steady temperature difference from which sample thermal conductivity can be determined. Calibration is required to give correct representation of changing heater resistance, system layer thicknesses and solid material thermal conductivities with temperature. In this preliminary study, methanol/water mixtures are measured at atmospheric pressure over the temperature range 30-50A degrees C. The results show that the device has produced a measurement accuracy of within 2.5% over the range of thermal conductivity and temperature of the tests. A relation between measurement uncertainty and the geometric and thermal properties of the system is derived and this is used to identify ways that error could be further reduced.

Experimental and Numerical Evaluation of Thermal Performance of Steered Fibre Composite Laminates

For Variable Stiffness (VS) composites with steered curvilinear tow paths, the fiber orientation angle varies continuously throughout the laminate, and is not required to be straight, parallel and uniform within each ply as in conventional composite laminates. Hence, the thermal properties (conduction), as well as the structural stiffness and strength, vary as functions of location in the laminate, and the associated composite structure is often called a “variable stiffness” composite structure. The steered fibers lead not only to the alteration of mechanical load paths, but also to the alteration of thermal paths that may
result in favorable temperature distributions within the laminate and improve the laminate performance. Evaluation of VS laminate performance under thermal loading is the focus of this chapter. Thermal performance evaluations require experimental and numerical analysis of VS laminates under different processing and loading conditions. One of the advantages of using composite materials in many applications is the tailoring capability of the laminate,
not only during the design phase but also for manufacturing. Heat transfer through variable conduction and chemical reaction (degree of cure) occurring during manufacturing (curing) plays an important role in the final thermal and mechanical performance, and shape of composite structures.

Coal combustion residues valorisation:Research and development on compressed brick production

This paper presents the results of an experimental investigation on compressive strength of unfired compressed brick obtained with coal combustion residues (CCRs) produced by the Niger Coal Society. Preliminary physical and optical (XRD and SEM) characterisation of coal slag, including lixiviation tests, have been carried out. Cement powder, lateritic clayey soil and sand have been chosen as stabilizing agents for bricks. 12 dosages have been tested and about 300 bricks have been produced with a hand-operated press. Results show uniaxial compressive strengths (UCSs) ranging from 4 MPa to 27 MPa for the highest cement stabilisation ratio. UCS higher than 7.5 MPa have been observed for stabilisation with 20% of laterite +10% cement after 45 days of curing. Obtained bricks showed good mechanical resistance and low weight. No health threat has been detected for the obtained samples. Study developments are oriented towards the analysis of Pozzolanic properties of CCRs, properties of hydrated lime stabilisation, thermal properties and durability assessment.© 2012 Elsevier Ltd. All rights reserved.

Thermo-Mechanical Properties of Poly ε-Caprolactone/Poly L-Lactic Acid Blends: Addition of Nalidixic Acid and Polyethylene Glycol Additives Journal of the Mechanical Behavior of Biomedical Materials

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of Poly ε-caprolactone (PCL) with Poly l-lactic acid (PLLA), Nalidixic Acid (NA) and Polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends.
Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity.
At the higher temperature the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.

Optimisation of a two-liquid component pre-filled acrylic bone cement system: A design of experiments approach to optimise cement final properties

The initial composition of acrylic bone cement along with the mixing and delivery technique used can influence its final properties and therefore its clinical success in vivo. The polymerisation of acrylic bone cement is complex with a number of processes happening simultaneously. Acrylic bone cement mixing and delivery systems have undergone several design changes in their advancement, although the cement constituents themselves have remained unchanged since they were first used. This study was conducted to determine the factors that had the greatest effect on the final properties of acrylic bone cement using a pre-filled bone cement mixing and delivery system. A design of experiments (DoE) approach was used to determine the impact of the factors associated with this mixing and delivery method on the final properties of the cement produced. The DoE illustrated that all factors present within this study had a significant impact on the final properties of the cement. An optimum cement composition was hypothesised and tested. This optimum recipe produced cement with final mechanical and thermal properties within the clinical guidelines and stated by ISO 5833 (International Standard Organisation (ISO), International standard 5833: implants for surgery—acrylic resin cements, 2002), however the low setting times observed would not be clinically viable and could result in complications during the surgical technique. As a result further development would be required to improve the setting time of the cement in order for it to be deemed suitable for use in total joint replacement surgery.

Spitzer observations of the asteroid-comet transition object and potential spacecraft target 107P (4015) Wilson-Harrington

Context: Near-Earth asteroid-comet transition object 107P/ (4015) Wilson-Harrington is a possible target of the joint European Space Agency (ESA) and Japanese Aerospace Exploration Agency (JAXA) Marco Polo sample return mission. Physical studies of this object are relevant to this mission, and also to understanding its asteroidal or cometary nature. Aims: Our aim is to obtain significant new constraints on the surface thermal properties of this object. Methods: We present mid-infrared photometry in two filters (16 and 22 μm) obtained with NASA's Spitzer Space Telescope on February 12, 2007, and results from the application of the Near Earth Asteroid Thermal Model (NEATM). We obtained high S/N in two mid-IR bands allowing accurate measurements of its thermal emission. Results: We obtain a well constrained beaming parameter (η = 1.39±0.26) and obtain a diameter and geometric albedo of D = 3.46±0.32 km, and pV = 0.059±0.011. We also obtain similar results when we apply this best-fitting thermal model to single-band mid-IR photometry reported by Campins et al. (1995, P&SS, 43, 733), Kraemer et al. (2005, AJ, 130, 2363) and Reach et al. (2007, Icarus, 191, 298). Conclusions: The albedo of 4015 Wilson-Harrington is low, consistent with those of comet nuclei and primitive C-, P-, D-type asteorids. We establish a rough lower limit for the thermal inertia of W-H of 60 Jm-2s-0.5 K-1 when it is at r = 1 AU, which is slightly over the limit of 30 Jm-2 s-0.5 K-1 derived by Groussin et al. (2009, Icarus, 199, 568) for the thermal inertia of the nucleus of comet 22P/Kopff.

A comparative study on the thermophysical properties for two bis[(trifluoromethyl)sulfonyl]imide-based ionic liquids containing the trimethyl-sulfonium or the trimethyl-ammonium cation in molecular solvents

Herein, we present a comparative study of the thermophysical properties of two homologous ionic liquids, namely, trimethyl-sulfonium bis[(trifluoromethyl) sulfonyl]imide, [S₁₁₁][TFSI], and trimethyl-ammonium bis[(trifluoromethyl)sulfonyl]imide, [HN₁₁₁][TFSI], and their mixtures with propylene carbonate, acetonitrile, or gamma butyrolactone as a function of temperature and composition. The influence of solvent addition on the viscosity, conductivity, and thermal properties of IL solutions was studied as a function of the solvent mole fraction from the maximum solubility of IL, x_s, in each solvent to the pure solvent. In this case, x_s is the composition corresponding to the maximum salt solubility in each liquid solvent at a given temperature from 258.15 to 353.15 K. The effect of temperature on the transport properties of each binary mixture was then investigated by fitting the experimental data using Arrhenius' law and the Vogel-Tamman-Fulcher (VTF) equation. The experimental data shows that the residual conductivity at low temperature, e.g., 263.15 K, of each binary mixture is exceptionally high. For example, conductivity values up to 35 and 42 mS·cm^-1 were observed in the case of the [S ₁₁₁][TFSI] + ACN and [HN₁₁₁][TFSI] + ACN binary mixtures, respectively. Subsequently, a theoretical approach based on the conductivity and on the viscosity of electrolytes was formulated by treating the migration of ions as a dynamical process governed by ion-ion and solvent-ion interactions. Within this model, viscosity data sets were first analyzed using the Jones-Dole equation. Using this theoretical approach, excellent agreement was obtained between the experimental and calculated conductivities for the binary mixtures investigated at 298.15 K as a function of the composition up to the maximum solubility of the IL. Finally, the thermal characterization of the IL solutions, using DSC measurements, showed a number of features corresponding to different solid-solid phase transitions, T_S-S, with extremely low melting entropies, indicating a strong organizational structure by easy rotation of methyl group. These ILs can be classified as plastic crystal materials and are promising as ambient-temperature solid electrolytes. © 2013 American Chemical Society.

The Influence of Cation Structure on the Chemical-Physical Properties of Protic Ionic Liquids

In this study we investigated the influence of five different cations on the physical-chemical properties of protic ionic liquids (PILs) based on bis(trifluoromethanesulfonyl)imide (TFSI-). We showed that the viscosities, ionic conductivities, densities and thermal properties of these PIL are strongly affected by the structure of the protic cation. Furthermore, the influence of the cation structure on the lithium coordination was investigated by Raman spectroscopy for all investigated PIL-based electrolytes for lithium-ion batteries (LIBs). This investigation clearly demonstrates, that the lithium average coordination number in PIL-based electrolytes is strongly affected by (ring) size and the number of protons on the cations structure and, more importantly, it might be significantly lower (more than 60 of that of electrolytes containing aprotic ionic liquids (AILs). Electrochemical performances of these PILs-based electrolytes were then also investigated to dress some conclusion on their applicability for LIB.