Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides as phase change materials for thermal energy storage

Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides have been produced as solid-liquid phase change materials via condensation of hexamethylene diamine with the respective acyl chlorides (lauroyl chloride, myristoyl chloride, and palmytoyl chloride) and were characterized by FT-IR, NMR, DSC, and TG analysis. Hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides crystallized due to structural symmetry and flexibility of long alkyl groups. They were characterized by DSC and FT-IR spectroscopy before and after thermal cycling to determine their thermal reliability. Phase change enthalpies were found 110.1 and −103.3 J g⁻¹ for hexamethylene dilauroyl amide (N,N′-hexamethylene didodecanamide), 116.9 and −110.4 J g⁻¹ for hexamethylene dimyristoyl amide (N,N′-hexamethylene ditetradecanamide), and 144.5 and −140.5 J g⁻¹ for hexamethylene dipalmytoyl amides (N,N′-hexamethylene dihexadecanamide) by DSC. The endurance of hexamethylene dilauroyl, dimyristoyl, and dipalmytoyl amides was studied by TG analysis.     

Galactitol hexa stearate and galactitol hexa palmitate as novel solid-liquid phase change materials for thermal energy storage

Galactitol has a melting point of 187.41 °C and a fusion enthalpy of 401.76 J g⁻¹. Its melting temperature is not suitable for many thermal energy storage applications although it has good latent heat storage capacity compared to the several traditional phase change materials (PCMs). The galactitol also has high supercooling degree as about 72 °C. These unfavorable properties limit the usage potential of galactitol in thermal energy storage applications. However, the phase change temperature and supercooling degree of galactitol can be reduced to a reasonable value and therefore its feasibility for energy storage systems can be increased. For this aim, in this study, galactitol hexa stearate (GHS) and galactitol hexa palmitate (GHP) were prepared as novel solid-liquid PCM by means of esterification reaction of the galactitol with palmitic acid and stearic acid. The GHP and GHS esters were characterized chemically using FT-IR and ¹H NMR techniques. By using DSC analysis method, the melting temperature and latent heat value of the PCMs were determined as 31.78 °C and 201.66 J g⁻¹ for GHP ester and 47.79 °C and 251.05 J g⁻¹ for GHS ester. Thermal cycling test showed that the prepared PCMs had good thermal reliability after thermal 1000 melting-freezing cycles. Thermogravimetric analysis (TGA) results revealed that the PCMs have good thermal stability over their working temperatures. In addition, thermal conductivity of the prepared PCMs was increased as about 26.3% for GHP and 53.3% for GHS by addition of 5 wt.% expanded graphite. Based on all results it can be concluded that the prepared GHP and GHS esters can be considered as promising solid-liquid PCMs for many energy storage applications such as solar energy storage, indoor temperature controlling in buildings, production of smart textile and insulation clothing due to their good energy storage properties.     

Preparation, thermal properties and thermal reliability of palmitic acid/expanded graphite composite as form-stable PCM for thermal energy storage

This study is focused on the preparation and characterization of thermal properties and thermal reliability of palmitic acid (PA)/expanded graphite (EG) composite as form-stable phase change material (PCM). The maximum mass fraction of PA retained in EG was found as 80 wt% without the leakage of PA in melted state even when it is heated over the melting point of PA. Therefore, the PA/EG (80/20 w/w%) composite was characterized as form-stable PCM. From differential scanning calorimetry (DSC) analysis, the melting and freezing temperatures and latent heats of the form-stable PCM were measured as 60.88 and 60.81 °C and 148.36 and 149.66 J/g, respectively. Thermal cycling test showed that the composite PCM has good thermal reliability although it was subjected to 3000 melting/freezing cycles. Fourier transformation infrared (FT-IR) spectroscopic investigation indicated that it has good chemical stability after thermal cycling. Thermal conductivities of PA/EG composites including different mass fractions of EG (5%, 10%, 15% and 20%) were also measured. Thermal conductivity of form-stable PA/EG (80/20 w/w%) composite (0.60 W/mK) was found to be 2.5 times higher than that of pure PA (0.17 W/mK). Moreover, the increase in thermal conductivity of PA was confirmed by comparison of the melting and freezing times of pure PA with that of form-stable composite. Based on all results, it was concluded that the form-stable PA/EG (80/20 w/w%) has considerable latent heat energy storage potential because of its good thermal properties, thermal and chemical reliability and thermal conductivity.     

Cellulose-based solid-solid phase change materials synthesized in ionic liquid

A series of cellulose graft poly(ethylene glycol) (cellulose-graft-PEG) copolymers as phase change materials (PCMs) were synthesized in ionic liquid by using 4, 4-diphenylmethane diisocyanate as coupling reagent. FTIR and ¹H NMR characterized the structure of the copolymers. Differential scanning calorimetry (DSC) indicated that the copolymers showed phase transitions with large thermal storage density, and the phase change temperature is in the range of 40-60 °C. The transition temperature and enthalpy can be tailored by changing the molecular weight and the content of poly(ethylene glycol) (PEG) side chains. The copolymers are solid-solid PCMs with good thermal stability. Expanded graphite (EG) with 2, 5 and 10 wt% was added to the PCMs to improve the thermal conductivity. It was found that the thermal conductivity enhanced significantly with increasing EG content. The cellulose-graft-PEG/EG composite PCMs have potential applications in thermal energy storage and temperature control.     

High latent heat storage and high thermal conductive phase change materials using exfoliated graphite nanoplatelets

Using exfoliated graphite nanoplatelets (xGnP), paraffin/xGnP composite phase change materials (PCMs) were prepared by the stirring of xGnP in liquid paraffin for high electric conductivity, thermal conductivity and latent heat storage. xGnP of 1, 2, 3, 5 and 7 wt% was added to pure paraffin at 75 °C. Scanning electron microscopy (SEM) morphology showed uniform dispersion of xGnP in the paraffin wax. Good dispersion of xGnP in paraffin/xGnP composite PCMs led to high electric conductivity. The percolation threshold of paraffin/xGnP composite PCMs was between 1 and 2 wt% in resistivity measurement. The thermal conductivity of paraffin/xGnP composite PCMs was increased as xGnP loading contents. Also, reproducibility of paraffin/xGnP composite PCMs as continuous PCMs was manifested in results of electric and thermal conductivity. Paraffin/xGnP composite PCMs showed two peaks in the heating curve by differential scanning calorimeter (DSC) measurement. The first phase change peak at around 35 °C is lower and corresponds to the solid-solid phase transition of the paraffin, and the second peak is high at around 55 °C, corresponding to the solid-liquid phase change. The latent heat of paraffin/xGnP composite PCMs did not decrease as loading xGnP contents to paraffin. xGnP can be considered as an effective heat-diffusion promoter to improve thermal conductivity of PCMs without reducing its latent heat storage capacity in paraffin wax.     

Preparation, characterization, and thermal properties of microencapsulated phase change material for thermal energy storage

This study is focused on the preparation, characterization, and determination of thermal properties of microencapsulated docosane with polymethylmethacrylate (PMMA) as phase change material for thermal energy storage. Microencapsulation of docosane has been carried out by emulsion polymerization. The microencapsulated phase change material (MEPCM) was characterized using scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. Thermal properties and thermal stability of MEPCM were measured by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). DSC analysis indicated that the docosane in the microcapsules melts at 41.0 °C and crystallizes at 40.6 °C. It has latent heats of 54.6 and −48.7 J/g for melting and crystallization, respectively. TGA showed that the MEPCM degraded in three distinguishable steps and had good chemical stability. Accelerated thermal cycling tests also indicated that the MEPCM had good thermal reliability. Based on all these results, it can be concluded that the microencapsulated docosane as MEPCMs have good potential for thermal energy storage purposes such as solar space heating applications.     

Microencapsulated n-octacosane as phase change material for thermal energy storage

This study deals with preparation and characterization of polymethylmetracrylate (PMMA) microcapsules containing n-octacosane as phase change material for thermal energy storage. The surface morphology, particle size and particle size distribution (PSD) were studied by scanning electron microscopy (SEM). The chemical characterization of PMMA/octacosane microcapsules was made by FT-IR spectroscopy method. Thermal properties and thermal stability of microencapsulated octacosane were determined using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The melting and freezing temperatures and the latent heats of the microencapsulated octacosane as PCM were measured as 50.6 and 53.2 °C, 86.4 and −88.5 J/g, respectively, by DSC analysis. TGA analysis indicated that the microencapsulated octacosane degrade in two steps and had good chemical stability. Thermal cycling test shows that the microcapsules have good thermal reliability with respect to the accelerated thermal cycling. Based on the results, it can be considered that the microencapsulated octacosane have good energy storage potential.     

Evaluation of phase change materials for thermal regulation enhancement of building integrated photovoltaics

Regulating the temperature of building integrated photovoltaics (BIPV) using phase change materials (PCMs) reduces the loss of temperature dependent photovoltaic (PV) efficiency. Five PCMs were selected for evaluation all with melting temperatures ∼25 ± 4 °C and heat of fusion between 140 and 213 kJ/kg. Experiments were conducted at three insolation intensities to evaluate the performance of each PCM in four different PV/PCM systems. The effect on thermal regulation of PV was determined by changing the (i) mass of PCM and (ii) thermal conductivities of the PCM and PV/PCM system. A maximum temperature reduction of 18 °C was achieved for 30 min while 10 °C temperature reduction was maintained for 5 h at −1000 W/m² insolation.     

High-chain fatty acid esters of myristyl alcohol with odd carbon number: Novel organic phase change materials for thermal energy storage—2

A series of high-chain fatty acid esters of 1-tetradecanol (myristyl alcohol) were synthesized via esterification of 1-tridecanoic, 1-pentadecanoic, 1-heptadecanoic and 1-nonadecanoic acids under vacuum and in the absence of catalyst. The esterification reactions were controlled by FT-IR spectroscopy. Differential scanning calorimeter (DSC) and thermo-gravimetric analyzer (TGA) were intensively used to determine the thermal properties of the presented novel organic phase change materials (PCM). The thermal properties were given in terms of phase change temperature, enthalpy, specific heat (C_p) and thermal decomposition temperature with related statistical calculations. The thermal reliability of the synthesized PCMs, which is an important property for utilization, was determined via measuring the change in thermal properties after 1000 thermal cycles. The DSC analyses indicated that the melting points of the novel organic PCMs were between 40 and 50 °C with phase change enthalpy above 200 kJ/kg. The results showed that these thermal storage materials were favorable for low temperature heat transfer applications with superior thermal properties and reliability among the known PCMs.     

High-chain fatty acid esters of myristyl alcohol with even carbon number: Novel organic phase change materials for thermal energy storage—1

High-chain fatty acid esters have not been investigated for their thermal properties as phase change materials (PCMs) in thermal energy storage. A series of high-chain fatty acid esters of myristyl alcohol (1-tetradecanol) were synthesized via esterification of lauric, myristic, palmitic, stearic and arachidic acids under vacuum and in the absence of any catalyst. The esterification reactions were studied by FT-IR spectroscopy. A differential scanning calorimeter (DSC) and a thermo-gravimetric analyzer (TGA) were intensively used to determine the thermal properties of the introduced thermal storage materials. The thermal properties were given in terms of phase change temperature, enthalpy, specific heat (C_p) and thermal decomposition temperature with related statistical data. The thermal reliability of the novel organic PCMs was investigated by thermal cycling with 1000 thermal cycles with respect to the thermal properties of the original synthesized PCMs. In addition to the synthesized esters, one commercial product was also investigated. The DSC analyses indicated that the melting points of the novel organic PCMs were between 38 and 53 °C with phase change enthalpy above 200 kJ/kg. The effect of chemical structure of the materials on thermal properties was also discussed. The results showed that these materials were favorable for low temperature heat transfer applications with superior thermal properties and reliability.     

Preparation of a new thermal regulating fiber based on PVA and paraffin

A new kind of thermal regulating fiber based on polyvinyl alcohol (PVA) and paraffin was prepared by wet composite spinning. In this fiber, PVA was the matrix or “sea” polymer to support the “island” paraffin, which was selected as phase change materials (PCMs) to store energy. Because of PVA's excellent barrier ability to nonpolar substances, paraffin can be remained in fiber stably. The thermal stabilities of fibers, thermal treating effects on fibers, mechanical properties of fibers, morphology and thermal properties of fibers were investigated by tensile strength tester, DSC and TGA. Results show that the thermal regulating fiber has the acceptable thermal stability when the content of paraffin in fiber was less than 30%. The best fiber properties of tensile strength 2.6 cN/dtex, breakage elongation: 19.9%, latent heat: 24.45 J/g can be achieved by manipulating the preparation process, and the latent heat of the fiber still remains 24.32 J/g after 25 times washing.     

Synthesis and Characterization of Disodium Hydrogen Phosphate Dodecahydrate-Lauric-Palmitic Acid Used for Indoor Energy Storage Floor Units

Organic and inorganic phase change materials(PCMs) are considered potential materials for thermal energy storage(TES) with different phase change characteristics. In this study, a novel organic-inorganic composite phase change material(PCM) called disodium hydrogen phosphate dodecahydrate-lauric-palmitic acid(D-LA-PACM) was prepared. Expanded graphite(EG) was selected as the support material, and the novel organic-inorganic form-stable PCM called D-LA-PAPCM/EG was prepared using the vacuum adsor...     

Preparation and thermal properties of polyethylene glycol/expanded graphite blends for energy storage

Expanded graphite is a promising heat transfer promoter due to its high conductivity, which improves the thermal conductivity of organic phase change materials. Moreover, it can also serve as supporting materials to keep the shape of the blends stable during the phase transition. After various investigation, the results showed that the maximum weight percentage of polyethylene glycol was as high as 90% in this paper without any leakage during the melting period, with the latent heat of 161.2 J g⁻¹ and the melting point of 61.46 °C. It was found that the value of the latent heat was related to the polyethylene glycol portion, increased with the increase in polyethylene glycol content. Moreover, the measured enthalpy of the composite phase change materials was proportional to the mass ratio of the polyethylene glycol component. The melting temperatures were almost the same with different ratios of composites. The conductivity of blends was improved significantly with the high value of 1.324 W m⁻¹ K⁻¹ compared to the pure polyethylene glycol conductivity of 0.2985 W m⁻¹ K⁻¹.     

Capric-myristic acid/vermiculite composite as form-stable phase change material for thermal energy storage

Phase change materials (PCMs) can be incorporated with building materials to obtain novel form-stable composite PCM which has effective energy storage performance in latent heat thermal energy storage (LHTES) systems. In this study, capric acid (CA)-myristic acid (MA) eutectic mixture/vermiculite (VMT) composite was prepared as a novel form-stable PCM using vacuum impregnation method. The composite PCM was characterized using scanning electron microscope (SEM) and Fourier transformation infrared (FT-IR) analysis technique. Thermal properties and thermal reliability of the composite PCM were determined by differential scanning calorimetry (DSC) analysis. The CA-MA eutectic mixture could be retained by 20 wt% into pores of the VMT without melted PCM seepage from the composite and therefore, this mixture was described as form-stable composite PCM. Thermal cycling test showed that the form-stable composite PCM has good thermal reliability and chemical stability although it was subjected to 3000 melting/freezing cycling. Thermal conductivity of the form-stable CA-MA/VMT composite PCM was increased by about 85% by introducing 2 wt% expanded graphite (EG) into the composite. The increase in thermal conductivity was confirmed by comparison of the melting and freezing times of the CA-MA/VMT composite with that of CA-MA/VMT/EG composite. The form-stable PCM including EG can be used as energy absorbing building material such as lightweight aggregate for plaster, concrete compounds, fire stop mortar, and component of interior fill for wallboards or hollow bricks because of its good thermal properties, thermal and chemical reliability and thermal conductivity.     

Thermal property measurement and heat transfer analysis of acetamide and acetamide/expanded graphite composite phase change material for solar heat storage

As a phase change material (PCM), acetamide (AC) can be a potential candidate for energy storage application in the active solar systems. Its utilization is however hampered by poor thermal conductivity. In this work, AC/expanded graphite (EG) composite PCM with 10 wt% (mass fraction) EG as the effective heat transfer promoter was prepared; its thermal properties were studied and compared with those of pure AC. Transient hot-wire tests showed that the addition of 10 wt% EG led to about five-fold increase in thermal conductivity. Investigations using a differential scanning calorimeter revealed that the melting/freezing points shifted from 66.95/42.46 °C for pure AC to 65.91/65.52 °C for AC/EG composite, and the latent heat decreased from 194.92 to 163.71 kJ kg⁻¹. In addition, heat storage and retrieval tests in a latent thermal energy storage unit showed that the heat storage and retrieval durations were reduced by 45% and 78%, respectively. Further numerical investigations demonstrated that the less improvement in heat transfer rate during the storage process could be attributed to the weakened natural convection in liquid (melted) AC because of the presence of EG.     

Micro-encapsulated paraffin/high-density polyethylene/wood flour composite as form-stable phase change material for thermal energy storage

Six novel polymer-based form-stable composite phase change materials (PCMs), which comprise micro-encapsulated paraffin (MEP) as latent heat storage medium and high-density polyethylene (HDPE)/wood flour compound as supporting material, were prepared by blending and compression molding method for potential latent heat thermal energy storage (LHTES) applications. Micro-mist graphite (MMG) was added to improve thermal conductivities. The scanning electron microscope (SEM) images revealed that the form-stable PCMs have homogeneous constitution and most of MEP particles in them were undamaged. Both the shell of MEP and the matrix prevent molten paraffin from leakage. Therefore, the composite PCMs are described as form-stable PCMs. The differential scanning calorimeter (DSC) results showed that the melting and freezing temperatures as well as latent heats of the prepared form-stable PCMs are suitable for potential LHTES applications. Thermal cycling test indicated the form-stable PCMs have good thermal stability although it was subjected to 100 melt–freeze cycles. The thermal conductivity of the form-stable PCM was increased by 17.7% by adding 8.8 wt% MMG. The results of mechanical property test indicated that the addition of MMG has no negative influence on the mechanical properties of form-stable composite PCMs. Taking one with another, these novel form-stable PCMs have the potential for LHTES applications in terms of their proper phase change temperatures, improved thermal conductivities, outstanding leak tightness of molten paraffin and good mechanical properties.     

Thermal characterization of phase change materials based on linear low-density polyethylene,paraffin wax and expanded graphite

Thermal characterization of Phase Change Materials (PCMs) based on linear low-density polyethylene (LLDPE), paraffin wax (W) and expanded graphite (EG) is reported in this paper. Investigated PCMs showed high potential for application in energy storage systems.The latent heat, L_m, sensible heat Q_sens, and the ability of the prepared PCMs to store and release thermal energy were investigated using specific home-made equipment based on the transient guarded hot plane method (TGHPT). The sensible heat of PCM containing 40 wt.% of paraffin wax was investigated in the temperature range 25–35 °C, they exhibited a drop in Q_sens from 31 to 24 J/g depending on the concentration of EG. A similar decrease in sensible heat with increased loading of EG was observed for PCMs containing 50 wt.% of EG.The storage and release of thermal energy during phase change which is associated with the latent heat of the materials were investigated within the temperature range 20–50 °C. PCMs containing 40 wt.% of paraffin wax exhibited latent heat of 36 J/g, whereas the latent heat of PCMs containing 50 wt.% of paraffin wax was 49 J/g. The addition of EG decreased the time needed to melt and solidify PCMs due to increase in thermal conductivity of PCMs with increase in EG content. This behavior was confirmed by the thermal conductivity measurements, where thermal conductivity increased from 0.252 for sample without EG to 1.329 W/m × °C for PCM containing 15 wt.% of EG.The reproducibility of storage and release of thermal energy by PCMs was demonstrated by subjecting them to repeated heating and cooling cycles (over 150 cycles).     

Novel gelatinous shape-stabilized phase change materials with high heat storage density

A series of polyol acetal derivatives were synthesized through condensation reactions of aromatic aldehyde with polyols, including sorbitol, mannitol, xylitol, and pentaerythritol. They were examined as gelators in the formation of paraffin-based shape-stabilized phase change materials (PCMs), in which 1,3:2,4-di-(4-methyl) benzylidene sorbitol (MDBS) exhibited excellent thermal stability. Three-dimensional netted structural phase change materials were obtained by paraffin doped with different gelators, which were thermally stable so that no leakage of paraffin occurs even under higher temperature than the melting point of paraffin. It was found that PCMs doped with 3 wt% expanded and exfoliated graphite (EG) exhibited better thermal conductivity, similar phase change temperature and heat storage density.     

Ag-coated polyurethane fibers membranes absorbed with quinary fatty acid eutectics solid-liquid phase change materials for storage and retrieval of thermal energy

The novel quinary fatty acid eutectic (CA-LA-MA-PA-SA) of capric acid, lauric acid, myristic acid, palmitic acid and stearic acid was successfully prepared with the mass ratio of 61.09/24.61/8.13/4.01/2.16. Thereafter, the innovative Ag-coated polyurethane (PU) fibers membranes with different concentrations of Ag, which were selected as a supporting material to adsorb the CA-LA-MA-PA-SA eutectics, were successfully fabricated through electrospinning followed by magnetron sputter. The energy dispersive X-ray confirmed that Ag nanoclusters were successfully deposited on the surface of PU fibers as a result of sputter coating. The observations of atomic force microscope indicated that the surface roughness of the PU fibers significantly increased with increase in coating time. The scanning electron microscope images demonstrated that the CA-LA-MA-PA-SA eutectics were uniformly distributed into the three-dimensional porous structures of uncoated and Ag-coated PU fibers membranes. Furthermore, the differential scanning calorimeter curves suggested that the CA-LA-MA-PA-SA/PU/Ag composites phase change materials (PCMs) possessed melting enthalpies about 110 kJ/kg and melting temperature around 17 °C. The absorption ratios of the CA-LA-MA-PA-SA eutectic in composite PCMs was approximately at 73.74%–83.18%. The investigation on thermal performance indicated that we achieved higher melting and freezing rates of the CA-LA-MA-PA-SA/PU/Ag composites PCMs by increasing coating time. In addition to this, after depositing Ag nanoparticles the melting and freezing times of composites PCMs were shortened to about 21%–65%.     

Lipid‐derived monoamide as phase change energy storage materials

One of the major shortcomings of current organic phase change materials (PCMs) is their relatively low melting points, typically below 80°C, which limits their integration into thermal energy storage (TES) systems. The present work was aimed at developing lipid‐derived PCMs with increased melting points which would be suitable for TES applications requiring higher melting points without compromising other key properties such as enthalpy. The introduction of an amide group into the structure of linear saturated fatty acids was used as a means to increase intermolecular interactions and therefore crystallization and melting points. A series of six linear monoamides with differing chain length and symmetry about the amide group were investigated for thermal stability, thermal transition, flow behavior, and crystal structure to establish the structure‐property relationships relevant to TES. The presence of the highly polar amide group in the aliphatic fatty acid–derived molecules resulted in notable improvement in performance compared with the analogous monofunctional molecules: Increases in melting points (79°C‐96°C) and high enthalpies of fusion (155‐201 J/g) were recorded. Fundamental relationships between structure, processing, and macroscopic physicochemical properties, never before elucidated, were revealed in the study. The study revealed a step‐like variation of macroscopic properties: a surprising outcome of the competition between intermolecular attractions, symmetry effects, and mass transfer limitations. The predictive structure‐function relationships established in this work will allow the straightforward engineering of monoamide architectures that can extend the range of organic PCMs and deliver thermal properties desirable for TES applications.