Synthesis and properties of microencapsulated n-octadecane with polyurea shells containing different soft segments for heat energy storage and thermal regulation

Microencapsulated n-octadecane with polyurea shells containing different soft segments were synthesized using 2,4-tolylene diisocyanate as an oil-soluble monomer and various amines as a water-soluble monomer through interfacial polycondensation. The Fourier transform infrared spectra and optical phase-contrast microscope confirmed that these polyurea shell materials were successfully fabricated onto the surface of n-octadecane. The morphological investigation suggested that the microcapsules synthesized using Jeffamine as the amine monomer had a smoother and more compact surface than those synthesized by ethylene diamine and diethylene triamine, and they possessed a larger particle size (about 16 μm) with a centralized size distribution as well. These microcapsules also exhibited much better phase change properties, higher encapsulation efficiency, and better anti-osmosis property than the other two. In addition, the microcapsules synthesized with a core/shell weight ratio of 70/30 are optimal when used as microencapsulated phase change materials.     

Preparation of n-tetradecane-containing microcapsules with different shell materials by phase separation method

Microcapsules for thermal energy storage and heat-transfer enhancement have attracted great attention. Microencapsulation of n-tetradecane with different shell materials was carried out by phase separation method in this paper. Acrylonitrile–styrene copolymer (AS), acrylonitrile–styrene–butadiene copolymer (ABS) and polycarbonate (PC) were used as the shell materials. The structures, morphologies and the thermal capacities of the microcapsules were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The ternary phase diagrams showed the potential encapsulation capabilities of the three shell materials. The effects of the shell/core ratio and the molecular weight of the shell material on the encapsulation efficiency and the thermal capacity of the microcapsules were also discussed. Microcapsules with melting enthalpy > 100 J/g, encapsulation efficiency 66–75%, particle size<1 μm were obtained for all three shell materials.     

Microencapsulation of phase change material in water dispersible polymeric particles for thermoregulating rubber composites—A holistic approach

Summary To avoid the leakage of phase change materials (PCM) to its surrounding, microencapsulation of PCM in a polymeric shell is highly desirable. These microcapsules ideally should provide a platform to store and release latent heat of the PCM without undergoing any physicochemical transformation of core (PCM) as well as shell (polymer) materials. Several characteristics such as heat transfer efficiency, thermal conductivity, water dispersibility, and durability of the PCM capsules are dependent on the nature of shell materials. In the present study, a random copolymer of poly (methyl methcrylate-co-2-hydroxyethyl methacrylate) poly (MMA-co-HEMA) with an optimum ratio of 75/25 (methyl methacrylate (MMA)/2-hydroxyethyl methacrylate (HEMA)) was used as shell material to encapsulate paraffin wax (PCM), using emulsion solvent evaporation method. The microcapsules of ~5-μm size with a shell thickness of ~0.8 μm with high encapsulation efficiency (~92.34%) and thermal storage capability (99.85%) were fabricated. In addition to ease of water dispersibility, PHEMA (poly(2-hydroxyethyl methacrylate)) containing water absorbable shells also exhibit enhanced thermal conductivity from 0.1 to 0.49 W/(m·K) at 25°C in wet state compared with the dry capsule. The capsules show good durability by displaying no significant change in thermal properties and water dispersibility after running through 500 heating/cooling cycles. To test the feasibility of this novel water dispersible microencapsulated PCM, these were mixed with natural rubber latex at various blend ratios, and their thermal behaviour was evaluated. The obtained rubber composite showed good thermoregulation property with enhanced mechanical strength.     

Preparation,characterization and thermal properties of PMMA/n-heptadecane microcapsules as novel solid–liquid microPCM for thermal energy storage

This study is focused on the preparation, characterization and thermal properties of microencapsulated n-heptadecane with polymethylmethacrylate shell. The PMMA/heptadecane microcapsules were synthesized as novel solid–liquid microencapsulated phase change material (microPCMs) by emulsion polymerization method. The chemical and thermal characterization of the microPCMs were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). The diameters of microPCMs were found in the narrow range (0.14–0.40 μm) under the stirring speed of 2000 rpm. The spherical surfaces of microPCMs were smooth and compact. The DSC results show that microPCMs have good energy storage capacity. Thermal cycling test showed that the microPCMs have good thermal reliability with respect to the changes in their thermal properties after repeated 5000 thermal cycling. TGA analyses also indicated that the microPCMs degraded in three steps and have good thermal stability. Based on all results, it can be considered that the PMMA/heptadecane microcapsules as novel solid–liquid microPCMs have good energy storage potential.     

Microencapsulation of phase change material with poly(ethylacrylate) shell for thermal energy storage

Microcapsules containing caprylic acid and polyethylacrylate shells were prepared using an emulsion polymerization technique for thermal energy storage applications. Ethylene glycol dimethacrylate was used as a crosslinking agent. The influence of the crosslinking agent concentration on the phase change properties of microcapsules was examined. The caprylic acid microcapsules (MicroPCMs) were analyzed by Fourier transform infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy, and differential scanning calorimetry. The results showed that microcapsules were synthesized successfully and that the best shell material:crosslinking agent concentration ratio was 1:0.2. The melting and freezing temperatures were measured through differential scanning calorimetry analysis and found to be 13.3 and 7.1°C, respectively. The melting and crystallization heats were determined to be 77.3 and ?77.0 kJ/kg, and the mean particle diameter was 0.64 μm. The thermal cycling tests of the microcapsules were performed for 400 heating/cooling cycles, and the results indicate that the synthesized microcapsules have good thermal reliabilities. Air stability test proved that the thermal properties and physical form of microcapsules were not affected by air. We recommend the prepared thermal, air, and chemically stable caprylic acid microcapsules for thermal energy storage applications as novel microPCM with latent heat storage capacities and properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Robust microencapsulated phase change materials in concrete mixes for sustainable buildings

For passive building applications, phase change materials (PCMs) are microencapsulated to avoid leakage of PCM from concrete structure. The primary challenge of using microencapsulated PCM (MPCM) is its weak shell structure. New MPCMs with different shell compositions to prevent breakage during mixing in fresh concrete are needed. In this study, free radical polymerization method to microencapsulate capric acid–myristic acid mixture as PCM with two different methyl methacrylate co‐polymers is proposed to produce robust MPCMs for building applications. Two new microcapsules (MPCM‐1 and MPCM‐2) having latent heats of 91.9 and 97.3 J/g were synthesized. SEM analyses showed the size of microcapsules being in the range of 400–850 nm for MPCM‐1 and 250–475 nm for MPCM‐2. Analyses also reveal that the shells of MPCMs were not harmed, as they were added into concrete mixes. The microsphere's geometry was preserved, and distribution was homogeneous. The MPCMs were also studied under thermal tests of 1000 heating/cooling cycles. No significant changes in thermal properties were observed after thermal cycling tests. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

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.     

Microencapsulation of n‐hexadecanol by in situ polymerization of melamine–formaldehyde resin in emulsion stabilized by styrene–maleic anhydride copolymer

Microcapsules with high thermal energy storage density were synthesized by in situ polymerization using melamine–formaldehyde resin as shell and n‐hexadecanol as core. Styrene–maleic anhydride (SMA) copolymer was synthesized by solution polymerization and hydrolyzed by NaOH to enhance its water solubility. This negatively charged SMA molecular copolymer self‐assembles on the surface of n‐hexadecanol droplets and facilitates the precipitation of positively charged melamine–formaldehyde prepolymer onto the droplet surface electrostatically. The morphology, chemical structure, composition, and thermal properties were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, and gas chromatography, respectively. The results show that the obtained microencapsulated phase‐change material (MePCM) dispersed individually with a spherical shape. Amount of emulsifier, ratio of shell–core material, and pH value of solution have a significant effect on the microencapsulation. Under optimum condition of 8% SMA to core material, 3.3:10 of shell–core material in feed, and polymerization under pH 4.0, spherical n‐hexadecanol MePCMs with core content of 79.1% and melting enthalpy of 171 J g^?1 at around 51°C were prepared. In situ polymerization based on SMA‐stabilized emulsion opens up a route to prepare a variety of microcapsules with aliphatic alcohol as core material. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation of pentadecane/poly(melamine‐urea‐formaldehyde) microcapsules for thermal energy storage applications

Phase change materials (PCMs) with suitable melting ranges for thermal energy storage applications are alkanes, paraffins, fatty acids, eutectic mixtures, and inorganic PCMs. Paraffinic hydrocarbons and fatty acids with low solubility in water are usually the preferred candidates. Pentadecane, which is an alkane hydrocarbon with the chemical formula C₁₅H₃₂, was used as PCM in this study. The pentadecane was microencapsulated with a poly(melamine‐urea‐formaldehyde (MUF)) shell for thermal energy storage. Pentadecane/poly(MUF) microcapsules were prepared by in situ polymerization method. The morphological analysis of pentadecane microcapsules was analyzed with scanning electron microscopy (SEM). Thermal properties of microcapsulated pentadecane were determined by differential scanning calorimetry (DSC). The results demonstrated that pentadecane/PUF microcapsules were prepared successfully, and they offer proper phase transition temperature range (8.7°C and 8.1°C) and heat enthalpy values (84.5 and ?88.2 kJ/kg) for thermal energy storage applications. According to the results, it was determined that pentadecane/poly(MUF) microcapsules have good potential for thermal energy storage applications.     

Preparation and characterization of poly(methyl methacrylate-co-divinylbenzene) microcapsules containing phase change temperature adjustable binary core materials

A series of phase change temperature adjustable microencapsulated phase change materials (micro-PCMs) were prepared by in situ polymerization method. The micro-PCMs possessed butyl stearate and paraffin as binary core materials, and poly(methyl methacrylate-co-divinylbenzene) (P(MMA-co-DVB)) copolymer as shell material. More importantly, compared with the conventional micro-PCMs, the binary core materials rendered the micro-PCMs a phase change temperature adjustable property by regulating the weight ratio of butyl stearate to paraffin. Scanning electron microscopy (SEM) photographs showed that micro-PCMs had relatively spherical profiles and compact surfaces with diameter ranging from 5–10 μm. Differential scanning calorimetry (DSC) results indicated that the binary core content in micro-PCMs was in a high range of 50–85%. Besides, these as-prepared micro-PCMs showed excellent thermal stability and they decomposed in two steps at considerably high temperatures above 200 °C.     

Synthetic and physical characterization of phase change materials microencapsulated by complex coacervation for thermal energy storage applications

This paper presents a comprehensive study of encapsulated phase change materials (PCMs). In order to investigate some synthesis parameters, microencapsulated paraffin with gelatin/gum Arabic wall system was prepared by the complex coacervation method and the performance of these microcapsules was evaluated by optical microscopy and differential scanning calorimetry. Further investigations were carried out on the impact of physical parameters on the melting time by studying the constrained melting transformation of an encapsulated PCM in a spherical shell subjected to a constant temperature media. Results indicate successful production of PCM microcapsules with high melting enthalpy (116 kJ/kg), and the effects of diameter and thermal conductivity on melting time of PCMs were demonstrated. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis,characterization and thermal properties of novel nanoencapsulated phase change materials for thermal energy storage

In this paper, nanocapsules containing n-octadecane with an average 50 nm thick shell of poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA), and a core/shell weight ratio of 80/20 were synthesized by the direct miniemulsion method, respectively. The average size of the capsules is 140 nm and 119 nm, respectively. The chemical structure of the sample was analyzed using Fourier Transformed Infrared Spectroscopy (FTIR). Crystallography of nanocapsules was investigated by X-ray diffractometer. The surface morphology was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The thermal properties and thermal stability of the sample were obtained from Differential Scanning Calorimeter (DSC) and Thermal Gravimetric Analysis (TGA). The temperatures and latent heats of melting and crystallizing of PEMA nanocapsule were determined as 32.7 and 29.8 °C, 198.5 and ?197.1 kJ/kg, respectively. TGA analysis indicated that PEMA/octadecane nanocapsule had good thermal stability. The nanocapsules prepared in this work had a much higher encapsulation ratio (89.5%) and encapsulation efficiency (89.5%). Therefore, the findings of the work lead to the conclusion that the present work provides a novel method for fabricating nanoencapsulated phase change material, and it has a better potential for thermal energy storage.     

Developing microencapsulated 12‐hydroxystearic acid (HSA) for phase change material use

Phase change materials (PCM) have an increasingly more important role as a thermal energy storage (TES) media. However, leakage problem of PCM causes limitation during their integration in TES systems. Therefore, the encapsulation of PCMs is attracting research interest to extend usage of PCMs in real TES applications in recent years. In this study, hydroxystearic acid (HSA) was encapsulated with polymethyl methacrylate (PMMA) and different PMMA comonomer shells via emulsion polymerization method for the first time in literature. HSA with high melting temperature range (74–78°C) can widen the scope of using PCMs, and the encapsulated form can make it more versatile. The chemical structures, morphologies, and thermophysical properties of capsules were determined by FT‐IR, SEM, DSC, TGA, and thermal infrared camera. Among the produced HSA capsule candidates, PMMA‐HEMA is the most promising with latent heat of 48.5 J/g with melting range of 47 to 85°C. SEM analysis indicated that the capsules have spherical shape with compact surface at nano‐micro (100–440 nm) size range; however, some capsules exhibited agglomeration.     

Phase change characteristic study of spherical PCMs in solar energy storage

This paper investigates the phase change behavior of 65 mol% capric acid and 35 mol% lauric acid, calcium chloride hexahydrate, n-octadecane, n-hexadecane, and n-eicosane inside spherical enclosures to identify a suitable heat storage material. Analytical models are developed for solidification and melting of sphere with conduction, natural convection, and heat generation. Both the models are validated with previous experimental studies. Good agreement was found between the analytical predictions and experimental study and the deviations were lesser than 20%. Heat flux release at the wall, cumulative energy release to the external fluid, are revealed for the best PCM. The influence of the size of encapsulation, initial temperature of the PCM, the external fluid temperature on solidified and molten mass fraction, and the total phase change time are also investigated.     

Mechanical response evaluation of microcapsules from different slurries

Thermal energy storage (TES) is one method to accumulate thermal energy. In TES, latent heat storage using phase change materials (PCM) has attracted a lot of interest, recently. Phase change slurries (PCS) consist on a carrier fluid binary system composed of water as the continuous phase and microencapsulated PCM as the dispersed phase. In this paper, two PCS to be used for TES in buildings were studied: Micronal^® DS 5007 X, from BASF company, and PCS28, a laboratory made sample. Both samples were characterized using particle size distribution and scanning electron microscopy, to observe the regular spherical microcapsules, the surface morphology, and the wall shell thickness of the microcapsules. Atomic force microscopy was used to analyze the force needed to break the PCS microcapsules, a critical parameter when the PCS are to be used in active pumpable systems, and also to evaluate the effective Young's modulus. Both samples were studied with the microcapsules broken and unbroken. The physicochemical and thermal properties were reported in a previous paper, and it can be concluded that both are proper candidates to be used in TES building heating and cooling applications, but the acrylic shell microcapsules present better breakage resistance to be used in active systems.     

Thermal buffering effect of a packaging design with microencapsulated phase change material

Temperature fluctuations during storage and transportation are the most important factors affecting quality and shelf life of food products. Phase change materials (PCM) with their isothermal characteristics are used to control temperature in various thermal operations. In this study, octanoic acid as PCM candidate was used in a packaging material design for thermal control of a food product. The PCM candidate was microencapsulated in different shell materials in our laboratory. Among the synthesized microcapsules, microencapsulated PCM (mPCM) (ΔHm = 42.9 J/g) with styrene polymer as the shell material was selected based on its properties of being cost effective and compatibility with human health. Thermal buffering effect of PCM in bulk and microencapsulated forms was tested in a packaging design with special PCM pockets. Results showed that packages with mPCM and bulk PCM provided 8.8 and 6 hours of thermal buffering effect for 160 g of chocolate compared with the package without PCM (reference package).     

A novel polynary fatty acid/sludge ceramsite composite phase change materials and its applications in building energy conservation

The preparation and characteristics of a composite phase change material (PCM) produced by incorporating polynary fatty acid eutectic mixture into sludge ceramsite were studied. According to Schröeder–Van Laar equation, five different kinds of polynary fatty acid eutectic mixture were prepared, and one of them, suitable for regulating room temperature, was absorbed into sludge ceramsite by vacuum impregnation method. The microstructures were observed by scanning electron microscope (SEM). The thermal properties and chemical structures were analyzed by differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectrometer, respectively. The durability or stability of the composite PCM was determined by heating–cooling cycles test, and the temperature regulation effect was tested by building models. The results indicated that polynary fatty acid eutectic mixture can be retained by 46 wt.% into the pores of sludge ceramsite without seepage. The melting temperature of composite PCM was 26.66 °C, and the corresponding melting enthalpy was 47.1 J/g, suitable to regulate building room temperature. The preparation of composite PCM was just a physical combination, and its chemical structures can remain stable in application process. In addition, model experiments showed that the prepared composite PCM can significantly reduce indoor temperature fluctuation, suitable for building energy conservation.     

Phase change microcapsules with lead tungstate shell for gamma radiation shielding and thermal energy storage

Novel microencapsulated phase change materials (MEPCMs) composed of the lead tungstate (PbWO₄) shell and paraffin core were designed for shielding of gamma radiation as well as thermal energy storage. Such MEPCMs were prepared via self‐assembly methods and in‐situ precipitation. The PbWO₄ shell with excellent photon attenuation can give the resulting MEPCMs an acceptable gamma radiation shielding capability. The chemical composition and structure of microcapsules samples were studied by X‐ray diffractometer (XRD) and Fourier‐transform infrared spectroscopy (FTIR). The effects of different core/shell mass ratios on the surface morphology and microstructure of the MEPCMs were determined by scanning electron microscopy (SEM), energy‐dispersive spectrometer (EDS), and transmission electronic microscopy (TEM). It was confirmed that the microcapsules exhibit a distinct core‐shell structure and a perfect spherical shape. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to present thermal stability and thermal‐storage capability of MEPCMs. A high‐purity germanium gamma spectrometer to measure the attenuation coefficient of the microcapsules for gamma rays showed that the MECPMs has good γ‐rays‐shielding property. The multifunction microcapsules in this study have great potential applications for building energy conservation as well as wearable personal protection in nuclear energy engineering.     

Development of an integrated pretreatment fractionation process for fermentable sugars and lignin: Application to almond (Prunus dulcis) shell

An environmentally friendly pretreatment process was developed to fractionate cellulose, hemicellulose and lignin from almond (Prunus dulcis) shells, consisting of hot water pretreatment (HWP) coupled with organic solvent (organosolv) pretreatment of water/ethanol (OWEP). This integrated pretreatment process proved more effective on the basis of yield of fermentable sugar and lignin separation compared with HWP alone, dilute acid pretreatment (DAP), ammonia pretreatment (AP), lime pretreatment LP, organosolv water/ethanol pretreatment (OWEP), and organosolv water/acetone pretreatment (OWAP). In the coupled hot water-organosolv process, hemicellulose sugars were recovered in the first residual liquid while varying amounts of cellulose was retained in the residual solid. The lignin fraction was obtained by simply adjusting the pH from the second liquid. The optimal two-stage process consisted of first HWP stage at 195 °C for 30 min, resulting in w_glucose = 95.4% glucose recovery yield and w_xylose = 92.2% xylose removal. The second organosolv OWEP stage was operated at 195 °C for 20 min, in ethanol in water mixtures of <phi>_ethanol = 50% and resulted in nearly w_glucose = 100% glucose recovery yield, w_xylose = 90% xylose and w_lignin = 61% lignin removal. After enzymatic hydrolysis, glucose yield was up to w_glucose = 95%, compared to 61% yield from untreated almond. Images obtained via scanning electron microscopy (SEM) highlighted the differences in almond structure from the varying pretreatment methods during biomass fractionation.