Reliable phase-change polyurethane crosslinked by dynamic ionic-bond crosslinking for thermal energy storage

The fabrication of phase-change materials (PCMs) for thermal energy storage is of great significance, since they combine the sustainable development of energy and human comfortable. Herein, a dynamically crosslinked PCM was successfully fabricated by the blending of complementary polyurethanes bearing carboxylic acid and tertiary amine through reversible ionic bonds via the acid–base reaction. The resultant PCM exhibited good crystalline property, which was confirmed by wide-angle X-ray diffraction and polarizing optical microscopy. Differential scanning calorimetry characterizations suggested that the prepared PCMs could reversibly store and release latent heat during heating and cooling process. The presence of physical crosslinks in PCM could maintain shape stable and had no deteriorate effect on the value of latent heat. Therefore, a high latent heat of 70 J/g was obtained within the temperature range of 13.2–45.4 °C. This good thermal storage ability remained constant even after 100 consecutive heating/cooling cycles. Thermogravimetric analysis results provided distinct evidence that the prepared PCM has an outstanding thermal stability with the onset decomposition temperature higher than 250 °C. The combined thermal storage ability and thermal reliability endow the PCM promising application as solar energy storage, waste heat utilization, and thermal protection coatings or adhesives. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48213.     

Novel phase change materials based on fatty acid eutectics and triallyl isocyanurate composites for thermal energy storage

In this study, a series of dimension‐stabilized fatty acid eutectics and triallyl isocyanurate (TAIC) composite phase change materials were prepared via in situ reaction by blending the fatty acids and TAIC, in which the fatty acids were introduced as a phase change material (PCM), and TAIC performed as a supporting material by self‐crosslinking. Fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy (SEM), and thermogravimetric analysis were applied to investigate the chemical structure, crystalline properties, phase transition behavior, microstructure, and thermal stability of the composites. The results indicated that the composite possessed excellent thermal reliability and heat storage durability even after 300 heating–cooling cycles. Moreover, the composites had applicable phase transition temperatures in the range of 26–40 °C and satisfying latent heat storage capacities of higher than 110 J/g. The SEM images showed that the particle size of the nanoparticles of the composites was about 200 nm after treatment. The dimensional measurement of the composites proved a high service temperature of 100 °C, indicating that the composites were promising for thermal energy storage materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44866.     

Preparation and thermal energy storage properties of poly(n‐butyl methacrylate)/fatty acids composites as form‐stable phase change materials

This work is focused on the preparation, characterization, and determination of thermal energy storage properties of poly(n‐butyl methacrylate) (PnBMA)/fatty acid composites as form‐stable phase change material (PCM). In the composite materials, the fatty acids act as latent heat storage material whereas PnBMA serves as supporting material, which prevents the leakage of the melted fatty acids. The maximum encapsulation ratio for all fatty acids was found to be 40 wt%. The composites that do not allow PCM leakage in melted state were identified as form‐stable PCMs. The compatibility of fatty acids with PnBMA is investigated by optical microscopy (OM) and Fourier Transform Infrared (FT‐IR) spectroscopy. Thermal properties and thermal reliability of the form‐stable composite PCMs were determined using differential scanning calorimetry (DSC). DSC analysis revealed that the form‐stable composite PCMs had melting temperatures between 29.62°C and 53.73°C and latent heat values between 67.23 J/g and 87.34 J/g. Thermal stability of the composite PCMs was studied by thermal gravimetric (TG) analysis and the results indicated that the form‐stable PCMs had good thermal stability. In addition, thermal cycling test showed that the composite PCMs had good thermal reliability with respect to the changes in their thermal properties after accelerated 5,000 thermal cycling. On the basis of all results, it was also concluded that the prepared form‐stable composite PCMs had important potential for many thermal energy storage applications such as solar space heating of buildings by using wallboard, plasterboard or floors integrated with PCM. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Performance of form-stable myristic acid/polymethyl methacrylate composite phase-change material coated with nitrile butadiene rubber/polyacrylic acid layered coatings

The aim of this work is to determine the effect of coating and blending composition of myristic acid (MA) with polymethyl methacrylate (PMMA) on the latent heat and thermal stability of phase change material (PCM). Form-stable PCM (FSPCM) was prepared by blending MA with PMMA and then coating with nitrile butadiene rubber (NBR) and polyacrylic acid (PA) layers. This is the first attempt to coat the PCM with elastomeric latex. Leakage test results showed that addition of 20 wt% PMMA to the MA and NBR-PA coating layers could eliminate leakage in sample PCM8O. Tensile test results showed that NBR-PA coating material provide sufficient strength and elasticity to hold the PCM during the phase change process. Latent heat of melting and freezing of the form stable PCM80 is 107.56 J/g and 102.26 J/g, which is comparable with other results in the literature. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48642.     

Poly(styrene‐co‐maleic anhydride)‐graft‐fatty acids as novel solid–solid PCMs for thermal energy storage

A solid–solid phase change material (S‐SPCM) can store and release a specific amount of latent heat during its phase transition. In this regard, poly(styrene‐co‐maleic anhydride) (SMA)‐graft‐fatty acids (FA) copolymers were synthesized as novel S‐SPCMs for thermal energy storage (TES). The chemical structures of the SMA‐g‐FA copolymers were characterized by proton nuclear magnetic resonance (¹H NMR) and Fourier transform infrared (FT‐IR) spectroscopy techniques. The phase transformations of the copolymers form crystalline phase to amorphous phase were monitored using polarized optical microscopy (POM). The latent heat TES (LHTES) properties, thermal cycling reliability, and thermal stability of the S‐SPCMs were investigated by differential scanning calorimetry and thermogravimetric analysis methods. The SMA‐g‐FA copolymers produced as S‐SPCMs showed solid–solid phase transitions at about 40°C–60 °C range and had latent heat storage and release ability between 84 and 127 J/g, respectively. The S‐SPCMs had stable chemical structures and reliable LHTES characteristics even after 5,000 thermal cycling. They had reasonable thermal conductivity value changed in the range of 0.15–0.19 W/mK. Furthermore, it was concluded that the SMA‐g‐FA copolymers can be considered as promising S‐SPCMs for TES utilizations. POLYM. ENG. SCI., 59:E337–E347, 2019. © 2019 Society of Plastics Engineers     

Preparation and characterization of di‐hexadecanol maleic/triallyl isocyanurate cross‐linked copolymer as solid–solid phase change materials

Di‐hexadecanol maleic/Triallyl isocyanurate cross‐linked copolymers as a novel solid–solid phase change materials were successfully synthesized through bulk polymerization. TAIC is the skeleton and DM is a functional side chain that stores and releases heat during its phase transition process. Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, polarizing optical microscopy, differential scanning calorimetry, and thermogravimetry were employed to study the composition, chemical structure, crystalline properties, phase transition behaviors, and the thermal stability of the cross‐linked copolymers, respectively. The test results indicate that DM/TAIC cross‐linked copolymers have good thermal reliability and heat storage durability after 500 thermal cycles. The phase change temperatures of DM/TAIC cross‐linked copolymers were approximately 28.24–37.02°C, and it has high latent heat storage capacity of more than 83 J/g. At the same time, DM/TAIC cross‐linked copolymers have good thermal stability, and they can be processed or used in high temperature environments. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44065.     

Polymeric phase change composites for thermal energy storage

This article describes a group of thermal energy storage (TES) composites that combine TES and structural functionality. The composites are encapsulations of low melt temperature phase change materials (PCM) such as paraffin waxes in polymer matrices. Room temperature cured bisphenol‐A epoxy and styrene–ethylene–butylene–styrene (SEBS) polymers are chosen as matrix materials because of their excellent chemical and mechanical properties. The polymeric network structure in the composite encapsulates the PCMs, which transform from the solid to the liquid phase. The PCMs provide the energy storage function via the solid–liquid latent heat effect. The resulting composite exhibits dry‐phase transition in the sense that fluid motion of the PCM, when in the liquid phase, is inhibited by the structure of the polymer matrix. The polymer matrix is formulated to provide structural functionality. The latent heat, thermal conductivity and contact conductance, and structural moduli of composites having various PCM‐to‐matrix volume fractions are measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1240–1251, 2004     

Preparation of phase change materials microcapsules by using PMMA network‐silica hybrid shell via sol‐gel process

Encapsulation of phase change materials (PCM) using a poly(methyl methacrylate) network‐silica hybrid as the shell material has been developed. n‐Octadecane melted at 28°C was used as PCM. Based on the suspension polymerization process, the microcapsules were prepared successfully by mixing and by the reaction of ethylene glycol dimethacrylate with precopolymer solution with tetraethoxysilane (TEOS), whose resultant microcapsules had higher latent heat (ΔH = 151 J/g) than those without TEOS (ΔH = 88.3 J/g). The average size of the PCM microcapsules was about 10 μm. The silica content, n‐octadecane content, and latent heat of microcapsules were changed with varying ageing conditions, ageing time, and temperature. The highest amount of latent heat (ΔH = 178.9 J/g) and n‐octadecane content (73.3%) of the microcapsule were obtained when the inorganic/organic ratio of the microcapsule was 5%. It was difficult to increase n‐octadecane content (74% to 55.7–67.9%) and latent heat (180.5 J/g to 135.9–165.7 J/g) of the microcapsules by introducing different functional groups of coupling agents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Form-Stabilized Polyethylene Glycol/Palygorskite Composite Phase Change Material: Thermal Energy Storage Properties,Cycling Stability,and Thermal Durability

In this work, polyethylene glycol (PEG) as a phase change material (PCM) was incorporated with palygorskite (Pal) clay to develop a novel form-stable composite PCM (F-SCPCM). The Pal/PEG(40 wt%) composite was defined as F-SCPCM and characterized using SEM/EDS, FT-IR, XRD, DSC, and TGA techniques. The DSC results revealed that the F-SCPCM has a melting temperature of 32.5°C and latent heat capacity of 64.3 J/g for thermal energy storage (TES) applications. Thermal cycling test showed that the F-SCPCM had good cycling thermal/chemical stability after 500 cycles. The TGA data proved that that both cycled and non-cycled F-SCPCMs had considerable high thermal durability. Consequently, the created F-SCPCM could be considered as an additive material for production of green construction components with TES capability. POLYM. ENG. SCI., 60:909–916, 2020. © 2020 Society of Plastics Engineers     

Solid–solid phase‐change materials based on hyperbranched polyurethane for thermal energy storage

A hyperbranched polyol (HBP) was synthesized with poly(ethylene glycol) (PEG) as the core molecule and 2,2‐bis(hydroxymethyl) propionic acid as the chain extender. Then, a series of hyperbranched polyurethane phase‐change materials (HP‐PCMs) with different crosslinking densities was synthesized with isophorone diisocyanate and HBP as a molecular skeleton and PEG 6000 as a phase‐change ingredient. ¹H‐NMR, gel permeation chromatography, and Fourier transform infrared spectroscopy confirmed the successful synthesis of the HBP and HP‐PCMs. The polarization optical microscopy and wide‐angle X‐ray diffraction results show that the HP‐PCM exhibited good crystallization properties, but the crystallinity was lower than that of PEG 6000. The analysis results from differential scanning calorimetry indicated that the HP‐PCMs were typical solid–solid phase‐change materials with suitable phase‐transition temperatures. In addition, HP‐PCM‐3, with an appropriate degree of hyperbranched structure, possessed the highest thermal transition enthalpy of 123.5 J/g. Moreover, thermal cycling testing and thermogravimetric analysis showed that the HP‐PCMs exhibited good thermal reliability and stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45014.     

Poly(ethylene glycol)/poly(methyl methacrylate) blends as novel form‐stable phase‐change materials for thermal energy storage

In this study, we focused on the preparation and characterization of poly(ethylene glycol) (PEG)/poly(methyl methacrylate) (PMMA) blends as novel form‐stable phase‐change materials (PCMs) for latent‐heat thermal energy storage (LHTES) applications. In the blends, PEG acted as a PCM when PMMA was operated as supporting material. We subjected the prepared blends at different mass fractions of PEG (50, 60, 70, 80, and 90% w/w) to leakage tests by heating the blends over the melting temperature of the PCM to determine the maximum encapsulation ratio without leakage. The prepared 70/30 w/w % PEG/PMMA blend as a form‐stable PCM was characterized with optical microscopy and Fourier transform infrared spectroscopy. The thermal properties of the form‐stable PCM were measured with differential scanning calorimetry (DSC). DSC analysis indicated that the form‐stable PEG/PMMA blend melted at 58.07°C and crystallized at 39.28°C and that it had latent heats of 121.24 and 108.36 J/g for melting and crystallization, respectively. These thermal properties give the PCMs potential LHTES purposes, such as for solar space heating and ventilating applications in buildings. Accelerated thermal cycling tests also showed that the form‐stable PEG/PMMA blend as PCMs had good thermal reliability and chemical stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of erythritol–graphite foam phase change composite with enhanced thermal conductivity for thermal energy storage applications

Three-dimensional interconnected graphite composite foam as a heat conductive matrix was fabricated by using low cost polymeric precursors and polyurethane (PU) foam as carbon source and sacrificial macroporous template, respectively. Erythritol–graphite foam as a stable composite phase change material (PCM) was obtained by incipient wetness impregnation method. The thermophysical properties such as thermal diffusivity, specific heat, thermal conductivity and latent heat of the erythritol–graphite composite foam were measured. From the results, it was found that the thermal conductivity of the erythritol–graphite composite foam (3.77 W/mK) was enhanced 5 times as compared with that of pristine erythritol (0.72 W/mK). This enhancement can significantly reduce the charging and discharging times of the PCM storage system. There is no chemical reaction between erythritol and graphite as confirmed by X-ray diffractometer (XRD). The PCM/foam composite has a melting point of 118 °C and latent heat of 251 J/g which corresponds to the mass percentage (75 wt.%) of the erythritol within the composite foam. The obtained results confirmed the feasibility of using erythritol–graphite foam as a new phase change composite for thermal energy storage (TES) applications, thus it can contribute to the efficient utilization and recovery of solar heat or industrial waste heat.     

Eudragit S (methyl methacrylate methacrylic acid copolymer)/fatty acid blends as form‐stable phase change material for latent heat thermal energy storage

By composing (Eudragit S) with fatty acids (stearic acid (SA), palmitic acid (PA), and myristic acid (MA)), form‐stable phase change materials (PCMs), which can retain the same shape in a solid state even when the temperature of the PCMs is over the melting points of the fatty acids, are prepared. The compatibility of fatty acids with the Eudragit S is proved by microscopic investigation and infrared (FTIR) spectroscopy. The melting and crystallization temperatures and the latent heats of melting and crystallization of the form‐stable PCMs are measured by Differential Scanning Calorimetry (DSC) method. The maximum mass percentage of all fatty acids in the form‐stable PCMs is found as 70%, and no leakage of fatty acid is observed at the temperature range of 50–70°C for several heating cycles. Thermal properties obtained from the DSC analysis indicate that the Eudragit S/fatty acid blends as form‐stable PCM have great potential for passive solar latent heat thermal energy storage (LHTES) applications in terms of their satisfactory thermal properties and utility advantage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1402–1406, 2006     

Development of heat storage gypsum board with paraffin-based mixed SSPCM for application to buildings

Latent heat thermal energy storage using phase change materials (PCMs) is considered to be the method with the most potential to solve the energy shortage problem. In this study, paraffin-based mixed shape-stabilized PCM (SSPCM) (PBMS) was made by vacuum impregnation method. The prepared PBMS was added to gypsum powder as a fine aggregate. In the experiment, the n-hexadecane and n-octadecane was used as the PCM and the materials have latent heat capacities of 254.7 and 247.6 J/g, and melting points of 20.84 and 30.4 °C, respectively. The PBMS was prepared by an impregnation method in a vacuum, following the manufacturing process. The physical and thermal properties of the PBMS gypsum board were analyzed by Fourier transform infrared spectrometry (FTIS), differential scanning calorimetry, enthalpy analysis, and thermogravimetric analysis. From the Fourier transform infrared analysis, PBMS could be maintained in the structure of the gypsum board due to its physical rather than chemical bonding. From the specific heat and enthalpy analysis, the PBMS has high enthalpy and thermal inertia property. In addition, the gypsum board with PBMS has high latent heat capacity and high thermal efficiency.     

Facile preparation and thermal performances of hexadecanol/crosslinked polystyrene core/shell nanocapsules as phase change material

In this study, we report the synthesis of nanoencapsulated phase change material (PCM) with hexadecanol as core and crosslinked polystyrene (PS) as shell material via facile one‐pot emulsion polymerization and its thermal performances. By this method, no high shear homogenization is required to create nanocapsules in emulsion polymerization. The nanosized core/shell structure of the hexadecanol/PS capsules was confirmed by scanning electron microscopy and transmission electron microscope. Thermal performances of the nanoencapsulated PCM were determined using differential scanning calorimetry and thermogravimetry. The results indicated that the hexadecanol/PS nanocapsules had relatively high latent heat of fusion and good thermal stability, which make them attractive for thermal energy storage and heat transfer applications. POLYM. COMPOS., 35:2154–2158, 2014. © 2014 Society of Plastics Engineers     

聚乙二醇/涤纶接枝共聚固-固相转变贮热材料

为了制备热稳定性好、蓄热性能优异的固-固相转变材料(PCM),研究采用化学法合成了聚乙二醇(PEG)/涤纶(PET)PCM。实验结果表明,PEG/PET PCM的热力学性能与PEG的分子量、PEG/PET质量配比以及不同交联体系有关。化学接枝法合成的PEG/PET PCM,最大相变焓可达112.02 J/g,热稳定性提高,热滞后性减小,PEG/PET PCM在众多领域具有广泛应用。     

Phase change material with flexible crosslinking for thermal energy storage

The utilization of renewable energy through phase change materials (PCMs) is particularly attractive for the realization of sustainable society. Herein, a flexible but reliable solid–solid PCM was successfully synthesized by the integration of quadruple H-bonding crosslinks with polyethylene glycol (PEG)-based polyurethanes. The strong quadruple H-bonding from the dimerization of 2-ureido-4 [1H]-pyrimidinone (UPy) units could act as dynamic cross-links to maintain shape stability. PEG chains in flexible polymer network serve as phase change ingredients, affording thermal energy storage capacity. The physical crosslink density and phase change enthalpy can be adjusted. In contrast to chemical crosslinks, the physical crosslinks of UPy provide reprocessability of the prepared PCMs and show little hindrance on the crystallization of PEG chains. The chemical structure, phase transformation, crystallization, and thermal properties of prepared PCMs were characterized by fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction, polarizing microscope, and thermogravimetric analysis. DSC analysis shows that the prepared PCM can store 101.9 J g⁻¹ when PCMs undergo phase change process. Moreover, the accelerated thermal cycling test and leakage test are also conducted to illustrate the thermal reliability and shape-stable properties. These PCMs that possess high phase change enthalpy and outstanding reprocessability are alternative for solar energy collection and waste heat recovery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48497.     

Polyester-based phase change materials with flexible poly(ethylene glycol) chains for thermal energy storage

Phase change materials are capable of storing renewable energy in an economical, feasible, and green way. Here, novel polyester-based solid–solid phase change materials (PPCMs) are synthesized through solvent-free crosslinking polymerization. Poly(ethylene glycol) (PEG) is used as the phase change ingredient, while crosslinked polyester acts as the supporting material. One chain end of PEG reliably bonds with the rigid skeleton, while another chain end is movable. The combination of reliable crosslinked structures with flexible PEG chains endows the PPCMs with good thermal storage capacity and outstanding thermal reliability simultaneously. Fourier transform infrared spectroscopy is adopted to confirm the chemical structures of PPCMs. Their excellent crystalline properties are confirmed by wide-angle X-ray diffraction and polarizing optical microscopy (POM). Phase change properties are investigated using differential scanning calorimetry (DSC) and POM images. It is obvious in the DSC results that PPCMs have good thermal storage capacity in the range 18–63 °C with phase change enthalpy reaching 139.0 J/g. POM images vividly reveal the crystallization process of PPCMs. Additionally, thermal stability is studied using thermogravimetric analysis, and the results show that PPCMs are thermally stable up to 300 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47108.     

Flammability and thermal properties of high density polyethylene/paraffin hybrid as a form‐stable phase change material

In this study, form‐stable phase change material (PCM)–high density polyethylene (HDPE)/paraffin hybrid with different flame‐retardant systems are prepared by using twin‐screw extruder technique. This kind of form‐stable PCM is made up of paraffin (a dispersed phase change material) and a HDPE (a supporting material). Their structures and flammability properties are characterized by scanning electronic microscope (SEM) and cone calorimetry. Thermal stability is shown by thermogravimetry analysis (TGA) and its latent heat is given by differential scanning calorimeter (DSC) method. SEM results show that the HDPE forms a three‐dimensional net structure and the paraffin is dispersed in it. The peak of heat release rate (HRR) of the flame‐retardant form‐stable PCM decreases markedly. In TGA curves, although the onset of weight loss of flame‐retardant form‐stable PCMs occur at a lower temperature than that of form‐stable PCM, flame‐retardant form‐stable PCMs produce a large amount of char residue at 700°C. DSC results show that the addition of flame retardant has little effect on the phase change latent heat of PCM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1320–1327, 2006     

Photocrosslinked biobased phase change material for thermal energy storage

A series of novel photocrosslinked biobased shape‐stabilized phase change materials (PCMs) based on octadecanol, eicosanol and docosanol have been prepared by UV technique for the purpose of thermal energy storage applications. Epoxidized soybean oil was reacted with acrylic acid to form acrylated soybean oil (ASO). The structure and composition, cross‐section morphology, thermal stability performances and phase change behaviors of ASO and UV‐cured PCMs were examined by using Attenuated total reflection fourier transform infrared spectroscopy, thermogravimetric analysis system (TGA), scanning electron microscopy, and differential scanning calorimetry. The results indicate that the UV‐cured biobased PCMs possess perfect phase change properties and a suitable working temperature range. The heating process phase change enthalpy is measured between 30 and 68 J/g, and the freezing process phase change enthalpy is found between 18 and 70 J/g. The decomposition of UV‐cured PCMs started at 260 °C and reached a maximum of 430 °C. All the biobased UV‐cured PCMs improved latent heat storage capacity in comparison with the pristine ASO sample. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43757.