Preparation and thermal properties of fatty acids/CNTs composite as shape-stabilized phase change materials

A series of fatty acids/carbon nanotubes (CNTs) composite shape-stabilized PCMs were prepared through infiltration method by using the eutectic mixture of capric acid, lauric acid, and palmitic acid as phase change materials, multi-walled CNTs as a supporting material. Nitrogen adsorption–desorption curves and SEM images of composite shape-stabilized PCMs indicate that the eutectic mixture was effectively absorbed into the porous structure of the CNTs. DSC thermograms show that the composite fatty acids/CNTs possess good phase change behavior. And the latent heat of the sample absorbed with 80 wt% fatty acids can achieve 101.6 J g^?1 in the melting process and its phase change temperatures and latent heat almost remain unchanged in 30 times of thermal cycling. Moreover, the thermal conductivity of the composite materials are significantly improved (up to 0.6661 W m^?1 k^?1) due to the addition of the highly thermal conductive CNTs.     

Thermal performance and flammability of phase change material for medium and elevated temperatures for textile application

Thermal energy storage and insulation have potential applications in many fields such as incorporating phase change material (PCM) in textile materials for insulation in medium and elevated temperatures when the high heat flux 80–84 kW m^?2 results from flashover conditions in a firefighting environment. The feasibility of four selected PCMs is considered in this research. The lack of guidance of hazards of sugar alcohols as a potential PCM is analyzed from molecular structure point of view. The results showed that isomerism of PCMs has a tremendous influence on the flash point of PCMs and hence flammability. Differential scanning calorimeter thermal performance showed that the four candidate PCMs have a remarkable melting temperature and enthalpy of fusion. Different heating rates were observed (1.11, 0.43, and 0.095 %) in the melting temperatures: at 50, 20, and 5 °C·min^?1, respectively. Smaller heating rates are preferable for accurate data. PCMs also undergo degradation due to the high-temperature exposure. Although dulcitol and d-mannitol have the same molecular formula, dulcitol requires higher temperature for degradation than does d-mannitol, and this difference is around 26.08 K. The analysis of results showed that the position of functional group has tremendous influence on the thermal performance. Salt hydrates have a multistep thermal degradation and the lowest loss of mass compared with sugar alcohols. This is because salt hydrates have higher intermolecular forces, which make them undergo high thermal endothermic and exothermic processes.     

An investigation of melting/freezing characteristics of nanoparticle-enhanced phase change materials

The aim of this study is to investigate the melting/freezing characteristics of paraffin by adding Cu nanoparticles. Cu/paraffin composite phase change materials (PCMs) were prepared by a two-step method. The effects of Cu nanoparticles on the thermal conductivity and the phase change heat transfer of PCMs were investigated by the Hot Disk thermal constants analyzer and infrared monitoring methods, respectively. The maximum thermal conductivity enhancements up to 14.2% in solid state and 18.1% in liquid state are observed at the 2?wt% Cu/paraffin. The photographs of infrared monitoring suggest that the melting and freezing rates of Cu/paraffin are enhanced. For 1?wt% Cu/paraffin, the melting and freezing times can be saved by about 33.3 and 31.6%, respectively. The results provide that adding nanoparticles is an efficient way to enhance the phase change heat transfer of PCMs.     

Dispersing different nanoparticles in paraffin wax as enhanced phase change materials

Highly conductive nanoparticles were proposed to be dispersed into phase change materials (PCMs) such as paraffin wax for heat transfer enhancement. The mixture, often referred to as nanoparticle-enhanced phase change material (NePCM), has been studied extensively for latent heat energy storage but with conflicting results. This study attempts to understand this problem by investigating the stability of NePCMs under multiple thermal (melting–solidification) cycles, which has not been well explained in previous studies. We believe that stability of a NePCM is prerequisite for any experimental investigation of its thermal properties or application. In this study, paraffin wax was chosen as the base material. Three different types of nanoparticles were tested, i.e., multi-walled carbon nanotubes, graphene nanoplatelets, and aluminum oxide nanoparticles (Al₂O₃). The nanoparticles were dispersed into paraffin wax at varying mass fractions using mechanical dispersion methods (sonication, stirring) with and without different surfactants. Stability of different mixtures was investigated after consecutive thermal cycles performed in an environmental chamber. Significant coagulation and deposition of nanoparticles were found after a few thermal cycles regardless of the nanoparticle type, concentration, or dispersion method. Different boundary conditions in heating were also examined for their effects. None of these methods led to long-term stable NePCMs. The “negative” results from this study indicate that long-term stability of NePCM (at least for the paraffin wax and nanoparticles tested) remains a major challenge and requires further research with a multidisciplinary approach.

     

Thermal energy storage and retrieval properties of form-stable phase change nanofibrous mats based on ternary fatty acid eutectics/polyacrylonitrile composite by magnetron sputtering of silver

This paper demonstrated a novel magnetron sputtering method used for the improvement in thermal energy storage and retrieval rates of phase change materials (PCMs). The ten types of ternary fatty acid eutectics (i.e., CA–LA–MA, CA–LA–PA, CA–LA–SA, CA–MA–PA, CA–MA–SA, CA–PA–SA, LA–MA–PA, LA–MA–SA, LA–PA–SA and MA–PA–SA) were firstly prepared using five fatty acids such as capric acid (CA), lauric acid (LA), myristic acid (MA), palmitic acid (PA) and stearic acid (SA) and then selected as solid–liquid PCMs. Thereafter, magnetron sputter coating was used to deposit the functional silver (Ag) nanolayers onto the surface of electrospun polyacrylonitrile (PAN) nanofibrous mats serving as supporting skeleton. Finally, a series of composite PCMs were fabricated by adsorbing the prepared ternary eutectics into three-dimensional porous network structures of Ag-coated PAN membranes. The observations by EDX determined the formation of Ag nanolayers on the PAN nanofibers surface after magnetron sputtering. The SEM images illustrated that the Ag-coated PAN nanofibers appeared to have larger fiber diameter and rougher surface. Ag-coated PAN nanofibrous mats could effectively prevent the leakage of molten ternary eutectics and help maintain form-stable structure due to surface tension forces, capillary and nanoconfinement effects. The DSC results suggested that the phase change temperatures of the ternary fatty acid eutectics were obviously lower than those of individual fatty acids and their binary eutectics. The adsorption rates of ternary fatty acid eutectics in the composite PCMs were determined to be about 89–98 %. The thermal performance test indicated that the metallic coating of Ag dramatically improved the thermal energy storage and retrieval rates of the composite PCMs.     

Thermal properties characterization of two promising phase change material candidates

Solar absorption cooling is a wonderful method to provide cold energy by exploiting solar energy. Phase change materials (PCMs) that store latent thermal energy are indispensible in solar absorption cooling system. It is worthwhile to find new PCMs due to the demanding on the temperature of the stored thermal energy which in turn would power the absorption chiller. In this paper, two compounds: 1-bromo-2-methoxynaphthalene (compound 1) and 2,2′-diphenyl-4,4′-bi(1,3-dioxane)-5,5′-diol (compound 2), were selected as potential PCMs. Their thermal energy storage properties and thermal stability were characterized by differential scanning calorimetry and thermogravimetric analysis. The results showed that both compounds could be applied as good PCMs in solar absorption cooling systems. Compound 1 melted at 356.82 K with the ΔH of 98.81 J g^?1, while compound 2 melted in a broad temperature range with the melting point of 466.26 K and the ΔH of 101.4 J g^?1. Both compounds exhibited good thermal stability. Furthermore, the molar specific heat capacities of these two compounds were measured by temperature-modulated differential scanning calorimetry from 198.15 K to the temperature that they started to decompose, and the thermodynamic functions of [H _T–H _298.15] and [S _T–S _298.15] were calculated based on the specific heat capacities data.     

One-step synthesis of CuS-decorated MWCNTs/paraffin composite phase change materials and their light–heat conversion performance

Paraffin wax (PW) is a solid–liquid organic phase change material (PCM). However, the low thermal conductivity and poor light–heat conversion performance limit its feasibility in solar thermal storage applications. In this paper, CuS-decorated carboxyl multi-wall carbon nanotubes (MWCNTs)/PW light–heat conversion composite PCMs were prepared by one step. The structure and properties of the composite PCMs were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, differential scanning calorimeter, thermogravimetric analysis, coefficient of thermal conductivity, UV–visible–near infrared spectrometer and light–heat conversion testing. The results showed that the light–heat conversion performance of CuS–MWCNTs/PW composite PCMs were better than that of MWCNT/PW composite PCMs with the same mass fraction. Therefore, it is expected that this research will open up new avenues of study for the creation of advanced composite PCM with excellent light–heat conversion performance.     

Thermodynamic insights into n-alkanes phase change materials for thermal energy storage

n-Alkanes have been widely used as phase change materials (PCMs) for thermal energy storage applications because of their exceptional phase transition performance, high chemical stability, long term cyclic stability and non-toxicity. However, the thermodynamic properties, especially heat capacity, of n-alkanes have rarely been comprehensively investigated in a wide temperature range, which would be insufficient for design and utilization of n-alkanes-based thermal energy storage techniques. In this study, the thermal properties of n-alkanes (C₁₈H₃₈-C₂₂H₄₆), such as thermal stability, thermal conductivity, phase transition temperature and enthalpy were systematically studied by different thermal analysis and calorimetry methods, and compared with previous results. Thermodynamic property of these n-alkanes was studied in a wide temperature range from 1.9 K to 370 K using a combined relaxation (Physical Property Measurement System, PPMS), differential scanning and adiabatic calorimetry method, and the corresponding thermodynamic functions, such as entropy and enthalpy, were calculated based on the heat capacity curve fitting. Most importantly, the heat capacities and related thermodynamic functions of n-heneicosane and n-docosane were reported for the first time in this work, as far as we know. This research work would provide accurate and reliable thermodynamic properties for further study of n-alkanes-based PCMs for thermal energy storage applications.     

Thermo-physical characterization of some paraffins used as phase change materials for thermal energy storage

Three phase change paraffinic materials (PCMs) were thermophysically (phase-transition temperatures, latent heat, heat capacity at constant pressure, density, and thermal conductivity) investigated in order to be used as latent heat storage media in a pilot plant developed in Plovdiv Bulgaria. Raman structural investigation probes aliphatic character of the E53 sample, while the E46 and ECP samples contain also unsaturated components due to their Raman features within 1,500–1,700 cm^?1 range. Orthorhombic structure of the three PCMs was evidenced by the Raman modes at the 1,417 cm^?1. The highest latent heat value, ΔH, of phase transitions among the three materials was represented by summation of a solid order–disorder, and melting latent heat was encountered by the E53 paraffin, i.e., 194.32 J g^?1 during a μ-DSC scan of 1 °C min^?1. Conversely, the ECP composite containing ceresin component shows the lowest latent heat value of 143.89 J g^?1 and the highest thermal conductivity of 0.46 W m^?1 K^?1 among the three phase change materials (PCMs). More facile melt-disordered solid transition with the activation energy of 525.45 kJ mol^?1 than the lower temperature transition of disorder–order (E _a of 631.73 kJ mol^?1) during the two-step process of solidification for the E53 melt are discussed in terms of structural and molecular motion changes.     

Preparation and thermal properties of palmitic acid/polyaniline/copper nanowires form-stable phase change materials

Form-stable phase change materials (PCMs) with high thermal conductivity are essential for thermal energy storage systems, which in turn are indispensible in solar thermal energy applications and efficient use of energy. In this paper, a new palmitic acid (PA)/polyaniline (PANI) form-stable PCMs were prepared by surface polymerization. The highest loading of PA in the form-stable PCMs was 80 mass% with the phase change enthalpy (ΔH _melting) of 175 J g^?1. Copper nanowires (Cu NWs) were introduced to the form-stable PCM by mixing the Cu NWs with PA and ethanol prior to the emulsifying of PA in surfactant solution. The Cu NWs would remain intact in case the ethanol was eliminated before the PA/Cu NWs mixture was mixed with surfactant solution. Otherwise, the Cu NWs would be partially oxidized under the attack of ethanol and ammonium persulfate. The ΔH _melting of the form-stable PCMs containing Cu NWs decreased linearly with the increasing of Cu NWs loading. The ΔH _melting of the form-stable PCMs doped with 11.2 mass% Cu NWs was 149 J g^?1. The thermal conductivity of the form-stable PCMs could be effectively improved by Cu NWs. By adding 11.2 mass% Cu NWs, the thermal conductivity of the form-stable PCM could attain 0.455 W m^?1 K^?1.     

Development of a model for compensating the influence of temperature gradients within the sample on DSC-results on phase change materials

The use of phase change materials (PCMs) in thermal storage is not a new concept, but engineers are continually finding new ways to utilize them in a wide range of applications. A PCM takes advantage of high latent heat in the phase change process to store large amounts of heat while undergoing only a small change in temperature. This property makes PCMs suitable for thermal storage purposes in a wide range of engineering applications. Due to the nature of these applications, it is vital to have a precise knowledge of the thermal characteristics of any PCM. Unfortunately, due to the low thermal conductivities and high latent heats found in PCMs, current measuring tools such as differential scanning calorimetry, provide inconsistent results. This paper conjectures that these errors come from the effects of low thermal diffusivity samples as well as improper data analysis methods.     

Thermal conductivity enhancement of Ag nanowires on an organic phase change material

One of the greatest challenges in the application of organic phase change materials (PCMs) is to increase their thermal conductivity while maintaining high phase change enthalpy. 1-Tetradecanol/Ag nanowires composite PCM containing 62.73 wt% (about 11.8 vol%) of Ag nanowires showed remarkably high thermal conductivity (1.46 W m⁻¹ K⁻¹) and reasonably high phase change enthalpy (76.5 J g⁻¹). This behavior was attributed to the high aspect ratio of Ag nanowires, few thermal conduct interfaces, and high interface thermal conductivity of Ag nanowires in the composite PCM. These results indicated that Ag nanowires might be strong candidates for thermal conductivity enhancement of organic PCMs.     

Effect of phase change materials on the hydration reaction and kinetic of PCM-mortars

The phase change materials are considered an attractive way to reduce energy consumption thanks to their heat storage capacity. Their incorporation in the construction materials allows the energy to be an integral part of the building structure. Even though PCMs have shown their reliability from a thermal point of view, some drawbacks linked to their use were emphasized such as the loss of the compressive strength of the PCM-material. This paper attempts to provide an explanation by the investigation of the hydration kinetic of PCM-mortars. The semi-adiabatic Langavant test was adapted to this case. The numerical diffuse element method was used for the computation of the heat flux, which is a compulsory step for the determination of the hydration degree. The results showed a lower heat released by the PCM mortars compared to a control mortar as well as a delay in the hydration progress with the addition of PCMs.     

ASA/SEBS/paraffin composites as phase change material for potential cooling and heating applications in building

Phase change material (PCM) is able to melt and crystalize with a high heat of phase change at constant temperature, which provides new and green cooling and heating strategies for buildings. In this work, PCMs for buildings composed of acrylonitrile‐styrene‐acrylate copolymer (ASA), polystyrene‐b‐poly(ethylene/butylene)‐b‐polystyrene triblock copolymer (SEBS) and paraffin were fabricated by melt blending. The results of the accelerated leakage test indicated an excellent ability of PCMs to keep paraffin from leakage. Thermal properties suggested that the phase change enthalpy of PCMs increased with the increasing content of paraffin and their phase change temperature was close to the comfortable sensible temperature of human body, which made it quite suitable for building cooling and heating. Besides, PCMs presented excellent stability and reusability after several thermal cycling tests. The temperature test conducted with self‐designed cylindrical devices gave a more sufficient and direct demonstration of the cooling and heating effect. Remarkably, excellent cooling and heating performance (both as high as 15°C) of the composites could be obtained with the addition of paraffin. And the time span of the cooling and heating process was as long as 5 and 7.5 hours, respectively. Owing to its excellent cooling and heating capabilities, the ASA/SEBS/paraffin composites are of great potential to be applied in building temperature control.     

Form-stable electrospun nanofibrous mats as a potential phase change material

A series of Poly vinyl butyral–Poly (acrylic acid) (PVB-PAA) based form-stable phase change materials (PCMs) have been prepared for the use of thermal energy storage applications. Six types of formulations containing five different fatty alcohols were prepared by adding PVB to PAA. Using electrospinning to fabricate nanofibrous mats, our aim was to investigate their properties as form-stable PCMs. Fatty alcohols, 1-Tetradecanol, 1-Hexadecanol, 1-Octadecanol, 1-Eicosanol and 1-Docosanol, were added separately to base formulation. The structural characterization tests were performed by ATR-FTIR spectroscopy. Morphological tests were conducted using Scanning Electron Microscope (SEM). Thermal performances and phase change behaviors were tested by thermogravimetric analysis system (TGA) and differential scanning calorimetry (DSC). The heating cycle phase change enthalpy is measured between 223 and 241?J/g, and the freezing cycle phase change enthalpy is found between 215 and 239?J/g. The main decomposition PVB-PAA based PCMs started at 220?°C. This study suggested that PVB-PAA based PCMs possess well phase change properties and they were found to have an applicable temperature range. With the presented results these materials promise a great potential in thermal energy storage applications.     

Microstructural and thermal response evolution of metallic form-stable phase change materials produced from ball-milled powders

Journal of Thermal Analysis and Calorimetry - Phase change materials (PCMs) can store and release the latent heat associated with a phase transition, so they can be applied in thermal energy...     

Study on thermal properties of organic ester phase-change material embedded with silver nanoparticles

This study investigates the thermal properties of new silver nano-based organic ester (SNOE) phase-change material (PCM) in terms of latent heat capacity, thermal conductivity and heat storage and release capabilities experimentally. Spherical-shaped surface-functionalized crystalline silver nanoparticles (AgNP) prepared were embedded in mass proportions of 0.1 through 5.0 wt% into the pure (base) PCM. Experimental results reveal that dispersion of AgNP into PCM was effective, only physical and no chemical interaction between AgNP and PCM has been exhibited; thereby phase-change temperature of SNOE PCMs were acceptable. These are essential characteristics for SNOE PCMs which signified their thermal and chemical stability on long term. Test results suggest that while compared to pure PCM, degree of supercooling was reduced by 11.7–6.8 % for aforesaid mass proportions of AgNP, whereas latent heat capacities decreased by 7.88 % in freezing and 8.91 % in melting. The interdependencies between thermophysical properties in improving nucleation and growth rate of stable SNOE PCM crystals were signified and discussed. Thermal conductivity of SNOE PCMs were enhanced from 0.284 to 0.765 W m^?1 K^?1 which was expected to be a 10–67 % increase for the above mass loading of AgNP. Furthermore, for SNOE PCMs enhancement span in freezing and melting cycles was improved by 41 and 45.6 %, respectively. Similarly, cooling and melting times were reduced by 30.8 and 11.3 %, respectively. Embedded AgNP helps to achieve improved thermophysical and heat storage characteristics for SNOE PCMs, which in turn can be considered as a potential candidate for cool thermal energy storage applications.     

Polydopamine-coated metal-organic framework-based composite phase change materials for photothermal conversion and storage

The liquid leakage and weak solar absorption capacity of organic phase change materials (PCMs) seriously hinder the efficient utilization of solar energy and thermal energy storage. To address these issues, we prepared nanoporous metal organic framework (Ni-MOF) for the vacuum infiltration of paraffin wax (PW), followed by the coating of solar-absorbing functional polydopamine (PDA) on the surface of PW@MOF for photothermal conversion and storage. As an efficient photon harvester, PDA coating endows PW@MOF/PDA composite PCMs with excellent photothermal conversion and storage properties due to the robust broadband solar absorption capability in the UV–vis region. Resultantly, our prepared PW@MOF/PDA composite PCMs exhibit a high photothermal conversion and storage efficiency of 91.2%, while that of PW@MOF composite PCMs is only zero. In addition, PW@MOF/PDA composite PCMs also exhibit excellent thermal stability, shape stability, energy storage stability, and photothermal conversion stability. More importantly, this coating strategy is universal by integrating different MOFs and solar absorbers, showing the potential to accelerate the major breakthroughs of high-efficiency MOF-based photothermal composite PCMs in solar energy utilization.     

Thermal stability of carbon nanotubes

Heat capacities of the carbon nanotubes (CNTs) with different sizes have been measured by modulated temperature differential scanning calorimetry (MDSC) and reported for the first time. The results indicated the values of C _p increased with shortening length of CNTs when the diameters of CNTs were between 60 and 100 nm. However, the values of C _p of CNTs were not affected by their diameter when the lengths of CNTs were 1–2 um, or not affected by the length of CNTs when their diameters were below 10 nm. The thermal stabilities of the CNTs have been studied by TG-DTG-DSC. The results of TG-DTG showed that thermal stabilities of CNTs were enhanced with their diameters increase. With lengths increase, the thermal stabilities of CNTs increased when their diameters were between 60 and 100 nm, but there is a slight decrease when their diameters were less than 60 nm. The further DSC analyses showed both released heat and T _onset increased with the increase of CNTs diameters, which confirms the consistency of the results from both TG-DTG and DSC on CNTs thermal stability.     

Microwave-assisted synthesis of poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules

In this study, lauryl alcohol suitable for thermal energy storage applications was microencapsulated in a poly(urea-formaldehyde) shell. The microcapsules were prepared by microwave-assisted in situ polymerization. The morphology and particle size of the poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules(UF/LA PCESMs) were analyzed using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering. The latent heat storage capacities of lauryl alcohol and UF/LA PCESMs were determined using differential scanning calorimetry. The chemical composition of the microcapsules was characterized using Fourier transform infrared spectroscopy. All of the results show that UF/LA PCESMs were synthesized successfully and that the latent heat storage capacity and encapsulation efficiency were 156.0 J/g and 75.0%, respectively, and the diameter of each microcapsule was around 150 nm.