Fatty acid/poly(methyl methacrylate) (PMMA) blends as form-stable phase change materials for latent heat thermal energy storage

Fatty acids such as stearic acid (SA), palmitic acid (PA), myristic acid (MA), and lauric acid (LA) are promising phase change materials (PCMs) for latent heat thermal energy storage (LHTES) applications, but high cost is the most drawback which limits the utility area of them in thermal energy storage. The use of fatty acids as form-stable PCM will increase their feasibilities in practical LHTES applications due to reduced cost of the energy storage system. In this regard, a series of fatty acid/poly(methyl methacrylate) (PMMA) blends, SA/PMMA, PA/PMMA, MA/PMMA, and LA/PMMA were prepared as new kinds of form-stable PCMs by encapsulation of fatty acids into PMMA which acts as supporting material. The blends were prepared at different mass fractions of fatty acids (50, 60, 70, 80, and 90% w/w) to reach maximum encapsulation ratio. All blends were subjected to leakage test by heating the blends over the melting temperature of the PCM. The blends that do not allow leakage of melted PCM were identified as form-stable PCMs. The form-stable fatty acid/PMMA (80/20 wt.%) blends were characterized using optic microscopy (OM), viscosimetry, and Fourier transform infrared (FT-IR) spectroscopy methods, and the results showed that the PMMA was compatible with the fatty acids. In addition, thermal characteristics such as melting and freezing temperatures and latent heats of the form-stable PCMs were measured by using differential scanning calorimetry (DSC) technique and indicated that they had good thermal properties. On the basis of all results, it was concluded that form-stable fatty acid/PMMA blends had important potential for some practical LHTES applications such as under floor space heating of buildings and passive solar space heating of buildings by using wallboard, plasterboard or floor impregnated with a form-stable PCM due to their satisfying thermal properties, easily preparing in desired dimensions, direct usability without needing an add encapsulation and eliminating the thermal resistance caused by shell and thus reducing cost of LHTES system.     

Study on preparation and thermal properties of binary fatty acid/diatomite shape-stabilized phase change materials

The choice of fatty acids as shape-stabilized phase change materials (PCMs) will increase the feasibilities of PCMs in practical applications due to the low price of the fatty acids. Compounding different fatty acids for each other is an effective way to obtain a PCM with a suitable phase-transition temperature. In this study, a series of binary fatty acids composed by capric acid, lauric acid, palmitic acid and stearic acid for each other were prepared using the phase diagram thermal dynamics calculation method. Then these binary fatty acids are absorbed in four kinds of diatomites with different specific areas, which act as a supporting material, to prepare shape-stabilized PCMs. The prepared shape-stabilized PCMs are characterized by the Scanning electron microscope (SEM) and the differential scanning calorimetry (DSC) analysis method. The results show that there is an optimum absorption ratio between binary fatty acids and the diatomite. The latent heat of capric-lauric acid/diatomite decreases to 57% of that of capric-lauric acid, and the phase-transition temperature rises from 16.36 to 16.74 °C when the capric-lauric acid is absorbed in the diatomite. The prepared capric-lauric acid/diatomite composite PCM has proper melting temperatures and latent heat for thermal energy storage application in buildings.     

Numerical heat transfer studies of the fatty acids for different heat exchanger materials on the performance of a latent heat storage system

Theoretical investigations of fatty acids as a phase change material (PCM) for energy storage system have been conducted in this study. The selected fatty acids were capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. For the two-dimensional simulation model based on the enthalpy approach, calculations have been made for the melt fraction with conduction only. Glass, stainless steel, tin, aluminium mixed, aluminium and copper were used as heat exchanger materials in the numerical calculations. Theoretical results show that capric acid was found good compatibility with latent heat storage system. The large value of thermal conductivity of heat exchanger materials did not make significant contribution on the melt fraction.     

Some fatty acids used for latent heat storage: thermal stability and corrosion of metals with respect to thermal cycling

The present study includes thermal stability of some fatty acids as phase change materials (PCMs). The selected fatty acids were stearic, palmitic, myristic and lauric acid with melting temperatures between 40–63°C and industrial-grade with 90–95 % purity. Latent heat storage capacity and phase transition temperature of the PCMs were determined by Differential Scanning Calorimetry (DSC) technique as a function of after repeated thermal cycles such as 40, 410, 700 and 910. The present work also comprises the investigation of corrosion resistance of some construction materials to the fatty acids over a long period. The containment materials tested were stainless steel (SS 304 L), carbon steel (steel C20), aluminium (Al) and copper (Cu). Gravimetric analysis as mass loss (mg/cm²), corrosion rate (mg/day) and a microscopic or matellographic investigation were performed for corrosion tests after 910 thermal cycles. DSC measurements showed that all fatty acids investigated as PCMs have a good thermal stability as a function of latent heat and phase transition temperature range for an actual middle-term thermal energy storage utility. However, in long-term solar thermal applications, the palmitic acid and myristic acid may be considered more suitable PCMs than the others. From the gravimetric and metallographic results, it can be concluded that stainless steel (SS 304L) with chromium oxide (Cr₂O₃) surface layer and Al with aluminium oxide (Al₂O₃) surface layer are essentially compatible with the investigated fatty acids. Carbon steel (Steel C20) and Cupper (Cu) are only preferantially compatible with PCMs.     

Thermal Energy Storage Performance of Fatty Acids as a Phase Change Material

Thermal energy storage performance of fatty acids and a eutectic mixture as phase change materials (PCMs) has been investigated experimentally. The selected PCMs for this study were palmitic acid, myristic acid, stearic acid, and a mixture of stearic and myristic acids in eutectic combination ratio of 65.7 wt% myristic acid and 34.3 wt% stearic acid. The PCMs have a melting temperature range of 50.0°C to 61.20°C and a latent heat range of 162.0 J/g to 204.5 J/g. The inlet temperature and the mass flow rate of heat transfer fluid (HTF) were selected as experimental parameters to test the thermal energy storage performance of the PCMs. The transition times, temperature range, propagation of the solid-liquid interface, as well as heat flow rate characteristics of the employed cylindrical tube storage system were studied at varied experimental parameters. The experimental results show that the melting front moves to inward in the radial directions as well as in the axial directions from the top toward to the bottom of the PCM tube. It was observed that the convection heat transfer in the liquid phase plays an important role in the melting process. The changes in the studied HTF parameters have more effect on the melting processes than the solidification processes of the PCMs. The average heat storage efficiency calculated from data for all the PCMs is 51.5%, meaning that 48.5% of the heat actually was lost somewhere.     

Phase change and heat transfer characteristics of a eutectic mixture of palmitic and stearic acids as PCM in a latent heat storage system

The phase change and heat transfer characteristics of a eutectic mixture of palmitic and stearic acids as phase change material (PCM) during the melting and solidification processes were determined experimentally in a vertical two concentric pipes energy storage system. This study deals with three important subjects. First is determination of the eutectic composition ratio of the palmitic acid (PA) and stearic acid (SA) binary system and measurement of its thermophysical properties by differential scanning calorimetry (DSC). Second is establishment of the phase transition characteristics of the mixture, such as the total melting and solidification temperatures and times, the heat transfer modes in the melted and solidified PCM and the effect of Reynolds and Stefan numbers as initial heat transfer fluid (HTF) conditions on the phase transition behaviors. Third is calculation of the heat transfer coefficients between the outside wall of the HTF pipe and the PCM, the heat recovery rates and heat fractions during the phase change processes of the mixture and also discussion of the effect of the inlet HTF parameters on these characteristics. The DSC results showed that the PA–SA binary system in the mixture ratio of 64.2:35.8 wt% forms a eutectic, which melts at 52.3 °C and has a latent heat of 181.7 J g⁻¹, and thus, these properties make it a suitable PCM for passive solar space heating and domestic water heating applications with respect to climate conditions. The experimental results also indicated that the eutectic mixture of PA–SA encapsulated in the annulus of concentric double pipes has good phase change and heat transfer characteristics during the melting and solidification processes, and it is an attractive candidate as a potential PCM for heat storage in latent heat thermal energy storage systems.     

The thermal storage performance of mixtures consisting of liquid paraffin and fatty acids

The thermal storage performance of binary mixtures consisting of fatty acids and liquid paraffin (LP) was studied experimentally. The study is to look for the material with suitable phase transition temperature and high phase change latent heat. The phase transition temperatures of binary mixtures consisting of capric acid and other four kinds of fatty acid are between 20°C and 30°C, and the phase change latent heat is high. They are ideal phase change materials used in the wall. The binary mixtures consisting of stearic acid, palmitic acid, lauric acid (LA) and myristic acid have high phase transition temperatures, and they are not suitable to use in the wall. The phase transition temperatures of mixtures consisting of LP and LA are between 20°C and 30°C, and the phase change latent heat is high. They can be used in the wall. The thermal stability of fatty binary mixtures is good.     

Thermal performance of a eutectic mixture of lauric and stearic acids as PCM encapsulated in the annulus of two concentric pipes

Thermal performance characteristics of a eutectic mixture of lauric and stearic acids as phase change material (PCM) during the melting and solidification processes were determined experimentally in a vertical two concentric pipe-energy storage system. This study deals with three important subjects: The first one is to determine the eutectic composition ratio of the lauric acid (LA) and stearic acid (SA) binary system, and to measure its thermophysical properties by DSC. The second one is to establish the thermal characteristics of the mixture such as total melting and solidification times, the heat transfer modes in melted and solidified PCM, and the effect of Reynolds and Stefan numbers as inlet heat transfer fluid (HTF) conditions on the phase transition behaviors. The final one includes the calculations of the heat transfer coefficients between the outside wall of the HTF pipe and the PCM, and heat fractions during the melting and solidification processes of the mixture, and also the discussion of the effect of inlet HTF parameters on these characteristics. The LA–SA binary system in the mixture ratio of 75.5:24.5 wt % forms a eutectic, which melts at 37°C and has a latent heat of 182.7 J g⁻¹, and, thus, these properties make it an attractive phase change material used for passive solar space heating applications such as building and greenhouse heating with respect to the climate conditions. The experimental results indicated that the mixture encapsulated in the annulus of two concentric pipes has good thermal and heat transfer characteristics during the melting and solidification processes, and it has potential for heat storage in passive solar space heating systems.     

Electrospun ultrafine composite fibers of binary fatty acid eutectics and polyethylene terephthalate as innovative form‐stable phase change materials for storage and retrieval of thermal energy

In this study, four fatty acids of lauric acid (LA), myristic acid (MA), palmitic acid (PA), and stearic acid (SA) were selected to prepare six binary fatty acid eutectics of LA‐MA, LA‐PA, LA‐SA, MA‐PA, MA‐SA, and PA‐SA; thereafter, electrospun ultrafine composite fibers with the binary fatty acid eutectics encapsulated in the supporting matrices of polyethylene terephthalate (PET) were prepared as innovative form‐stable phase change materials for storage and retrieval of thermal energy. The morphological structures and thermal energy storage properties of the ultrafine composite fibers were characterized by scanning electron microscope (SEM) and differential scanning calorimeter (DSC), respectively. The SEM results indicated that the fibers had the cylindrical morphology with diameters of 1–2 µm; some had smooth surfaces, while others had wrinkled surfaces with grooves. The DSC results indicated that the phase transition temperatures of binary fatty acid eutectics were lower than those of individual fatty acids; the enthalpy values associated with melting and crystallization for the eutectics encapsulated in the composite fibers were considerably reduced, whereas there were no appreciable changes on the phase transition temperatures. Copyright © 2012 John Wiley & Sons, Ltd.     

Morphology and thermal properties of electrospun fatty acids/polyethylene terephthalate composite fibers as novel form-stable phase change materials

The ultrafine fibers based on the composites of polyethylene terephthalate (PET) and a series of fatty acids, lauric acid (LA), myristic acid (MA), palmitic acid (PA), and stearic acid (SA), were prepared successfully via electrospinning as form-stable phase change materials (PCMs). The morphology and thermal properties of the composite fibers were studied by field emission scanning electron microscopy (FE-SEM) and differential scanning calorimetry (DSC), respectively. It was found that the average fiber diameter increased generally with the content of fatty acid (LA) in the LA/PET composite fibers. The fibers with the low mass ratio maintained cylindrical shape with smooth surface while the quality became worse when the mass ratio is too high (more than 100/100). Moreover, the latent heat of the composite fibers increased with the increase of LA content and the phase transition temperature of the fibers have no obvious variations compared with LA. In contrast, both the latent heat and phase transition temperature of the fatty acid/PET composite fibers varied with the type of the fatty acids, and could be well maintained after 100 heating-cooling thermal cycles, which demonstrated that the composite fibers had good thermal stability and reliability.     

Fatty acids and their mixtures as phase-change materials for thermal energy storage

An analysis of thermal properties of fatty acids and their binary mixtures has shown that they are attractive candidates for latent heat thermal storage in space heating applications. In this study, the method of differential scanning calorimetry was used to determine the transition temperatures and latent heat of transition of the fatty acids and their binary mixtures. These properties are of prime importance in the design of a latent heat thermal storage system.The melting range of the fatty acids (capric, lauric, palmitic and stearic) was observed to be approximately from 30°C to 65°C. Their heat of transition was observed to have a range from approximately 153 to 182 J/g. The eutectic points were determined for the binary mixtures of the fatty acids. The melting points of the eutectics for the binary systems of capric-lauric, lauric-palmitic, lauric-stearic and palmitic-stearic acids were found to be 18°C, 32.7°C, 34°C and 51°C respectively. The corresponding heats of melting were 120, 145, 150 and 160 J/g, respectively. The fatty acids and their eutectic mixtures were examined with an infrared spectrophotometer to ascertain the polymorphic forms and material purities.     

Lauric and myristic acids eutectic mixture as phase change material for low‐temperature heating applications

Lauric acid (m.p.: 42.6°C) and myristic acid (m.p.: 52.2°C) are phase change materials (PCM) having quite high melting points which can limit their use in low‐temperature solar applications such as solar space heating and greenhouse heating. However, their melting temperatures can be tailored to appropriate value by preparing a eutectic mixture of lauric acid (LA) and myristic acid (MA). In the present study, the thermal analysis based on differential scanning calorimetry (DSC) technique shows that the mixture of 66.0 wt% LA forms a eutectic mixture having melting temperature of 34.2°C and the latent heat of fusion of 166.8 J g^?1. This study also considers the experimental establishment of thermal characteristics of the eutectic PCM in a vertical concentric pipe‐in‐pipe heat storage system. Thermal performance of the PCM was evaluated with respect to the effect of inlet temperature and mass flow rate of the heat transfer fluid on those characteristics during the heat charging and discharging processes. The DSC thermal analysis and the experimental results indicate that the LA–MA eutectic PCM can be potential material for low‐temperature solar energy storage applications in terms of its thermo‐physical and thermal characteristics. Copyright © 2005 John Wiley & Sons, Ltd.     

Stearic acid/polymethylmethacrylate composite as form-stable phase change materials for latent heat thermal energy storage

The aim of this research is to prepare of a novel form-stable composite phase change material (PCM) for the latent heat thermal energy storage (LHTES) in buildings, passive solar space heating or functional fluid by entrapping of SA into PMMA cell through ultraviolet curing dispersion polymerization. The composite PCM was characterized using scanning electron microscope (SEM) and Fourier transformation infrared (FT-IR) analysis technique. The results show that the form-stable microencapsulated PCM with core/shell structure was formed and the maximum encapsulated proportion of SA in the composite was 51.8 wt.% without melted PCM seepage from the composite. In the shape stabilized microencapsulated PCM, the polymer acts as supporting material to form the microcapsule cell preventing the leakage of PCM from the composite and the SA acts as a PCM encapsulated in the cell of PMMA resin. The oxygen atom of carbonyl group of skeleton is interacted with the hydrogen atom of hydroxyl group of SA. Thermal properties, thermal reliability and heat storage/release performance of the composite PCM were determined by differential scanning calorimetry (DSC), FT-IR and thermal cycling test analysis. The melting and freezing temperatures and the latent heats of the composite PCM were measured as 60.4 °C, 50.6 °C and 92.1 J/g, 95.9 J/g, respectively. The results of DSC, FT-IR and thermal cycling test are all show that the thermal reliability of the composite PCM has an imperceptible change. This conclusion indicates that the composite has a good thermal and chemical stability.     

Thermal conductivity and latent heat thermal energy storage characteristics of paraffin/expanded graphite composite as phase change material

This study aimed determination of proper amount of paraffin (n-docosane) absorbed into expanded graphite (EG) to obtain form-stable composite as phase change material (PCM), examination of the influence of EG addition on the thermal conductivity using transient hot-wire method and investigation of latent heat thermal energy storage (LHTES) characteristics of paraffin such as melting time, melting temperature and latent heat capacity using differential scanning calorimetry (DSC) technique. The paraffin/EG composites with the mass fraction of 2%, 4%, 7%, and 10% EG were prepared by absorbing liquid paraffin into the EG. The composite PCM with mass fraction of 10% EG was considered as form-stable allowing no leakage of melted paraffin during the solid–liquid phase change due to capillary and surface tension forces of EG. Thermal conductivity of the pure paraffin and the composite PCMs including 2, 4, 7 and 10 wt% EG were measured as 0.22, 0.40, 0.52, 0.68 and 0.82 W/m K, respectively. Melting time test showed that the increasing thermal conductivity of paraffin noticeably decreased its melting time. Furthermore, DSC analysis indicated that changes in the melting temperatures of the composite PCMs were not considerable, and their latent heat capacities were approximately equivalent to the values calculated based on the mass ratios of the paraffin in the composites. It was concluded that the composite PCM with the mass fraction of 10% EG was the most promising one for LHTES applications due to its form-stable property, direct usability without a need of extra storage container, high thermal conductivity, good melting temperature and satisfying latent heat storage capacity.     

An assessment of mixed type PCM-gypsum and shape-stabilized PCM plates in a building for passive solar heating

Thermal performance of two phase change material (PCM) composites, mixed type PCM-gypsum and shape-stabilized PCM plates, has been numerically evaluated in a passive solar building in Beijing with an enthalpy model. Effects of the melting temperature and phase transition zone of the PCM are analyzed and a comparison between the two types of PCM composites is performed. The results show that: (1) for the present conditions, the optimal melting temperature is about 21 °C; (2) PCM composites with a narrow phase transition zone provide better thermal performance; (3) both mixed type PCM-gypsum and shape-stabilized PCM plates effectively shave the indoor temperature swing by 46% and 56%, respectively; (4) the shape-stabilized phase change material (SSPCM) plates respond more rapidly than the mixed type PCM-gypsum and prove to be thermally more effective in terms of utilizing the latent heat.     

Heat transfer enhancement of fatty acids when used as PCMs in thermal energy storage

Phase change materials (PCM) used in latent heat storage systems usually have very low thermal conductivities. This is a major drawback in maintaining the required heat exchange rate between PCM and heat transfer fluid. This paper investigates the enhancement of the heat transfer between PCM and heat transfer fluid, using high thermal conductivity as additives like stainless steel pieces, copper pieces and graphite–PCM composite material. In the experiments, palmitic–lauric acid (80:20) (PL) and stearic–myristic acid (80:20) (SM) were used as PCMs. Test results show that heat transfer enhancement of copper pieces was better at 0.05 Ls^?1 flow rate compared to 0.025 Ls^?1. Using copper as an additive increased the heat transfer rate 1.7 times for melting and 3.8 times for freezing when flow rate was 0.050 Ls^?1. Decreasing the flow rate from 0.050 to 0.025 Ls^?1, increased the melting times 1.3 times and freezing times 1.8 times, decreasing heat transfer rates accordingly. The best result of heat transfer enhancement was observed for the PCM–graphite composite. However, changing the flow rate did not affect the heat transfer rate when graphite was used as additive. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

基于火积理论的多级套管式相变蓄热系统优化

本文基于最小火积耗散热阻原理,在考虑相变材料导热热阻以及非稳态传热过程的基础上,对多级套管式相变蓄热系统的融化温度进行了数值优化,获得了最优融化温度分布。在此基础上,研究了相变材料导热系数和传热管长度对最优融化温度、火积耗散热阻和平均蓄热速率的影响。研究结果表明,与现有理论优化方法相比,本文提出的数值优化方法具有更好的适用性;优化后多级套管式相变蓄热系统可有效提高相变蓄热系统的平均蓄热速率,降低火积耗散热阻;随着相变材料导热系数增大和传热管长度增加,多级套管式相变蓄热系统最优融化温度的温差愈加明显,其强化传热性能呈上升趋势。     

Lauric and palmitic acids eutectic mixture as latent heat storage material for low temperature heating applications

Palmitic acid (PA, 59.8 °C) and lauric acid (LA, 42.6 °C) are phase change materials (PCM) having quite high melting temperatures which can limit their use in low temperature solar applications such as solar space heating and greenhouse heating. However, their melting temperatures can be tailored to appropriate value by preparing a eutectic mixture of the lauric and the palmitic acids. In the present study, the thermal analysis based on differential scanning calorimetry (DSC) technique shows that the mixture of 69.0 wt% LA and 31 wt% PA forms a eutectic mixture having melting temperature of 35.2 °C and the latent heat of fusion of 166.3 J g⁻¹. This study also considers the experimental determination of the thermal characteristics of the eutectic mixture during the heat charging and discharging processes. Radial and axial temperature distribution, heat transfer coefficient between the heat transfer fluid (HTF) pipe and the PCM, heat recovery rate and heat charging and discharging fractions were experimentally established employing a vertical concentric pipe-in-pipe energy storage system. The changes of these characteristics were evaluated with respect to the effect of inlet HTF temperature and mass flow rate. The DSC thermal analysis and the experimental results indicate that the LA–PA eutectic mixture can be a potential material for low temperature thermal energy storage applications in terms of its thermo-physical and thermal characteristics.     

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.