The effect of interface debonding behaviors on the mechanical properties of microPCMs/epoxy composites

Microcapsules containing phase change materials (microPCMs) can be filled in polymeric matrix forming smart temperature‐controlling composites. The aim of this study was to investigate the relationship between the interface behaviors and the mechanical properties of methanol‐melamine‐formaldehyde shell microPCMs containing paraffin/epoxy matrix composites. The typical microPCMs with core/shell ratio of 2/1 shapely decreased their average diameter from 26.0 ± 1.5 to 13.8 ± 3.4 μm with the increasing of stirring speed from 1,000 to 3,000 r min⁻¹. But, both the thickness and yield point of shells had a little variation. Young's modulus of composites was almost independent on the particle size of microPCMs with lower volume fractions (5%–10%). For composites with higher microPCMs loading (20%–30%), there was a slight decrease in modulus with increasing particle size. The data of tensile strength decreased obviously with the increasing of the average diameter of microcapsules for composite samples with the same particle loading. A repeated heat‐transmission treatment was applied to enhance the interface debonding. The results show that the violent thermal transmission had decreased the mechanical properties of microPCMs/epoxy composites. The scanning electron microscopy morphologies had also proved that these phenomena attributed to the interphase separation and cracks. Moreover, a semiexperiential conclusion is that the increasing of interface area of composites will at the same time give more structure defects leading to poor mechanical properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and characterization of flame retardant phase change materials by microencapsulated paraffin and diethyl ethylphosphonate with poly(methacrylic acid‐co‐ethyl methacrylate) shell

Microcapsules containing paraffin and diethyl ethylphosphonate (DEEP) flame retardant with uncrosslinked and crosslinked poly (methacrylic acid‐co‐ethyl methacrylate) (P(MAA‐co‐EMA)) shell were fabricated by suspension‐like polymerization. The surface morphologies of the microencapsulated phase change materials (microPCMs) were studied by scanning electron microscopy. The thermal properties and thermal stabilities of the microPCMs were investigated by differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The flame retarding performances of the microcapsule‐treated foams were calculated by using an oxygen index instrument. The DSC results showed that the crosslinking of the polymer shell led to an increase in the melting enthalpies of the microcapsule by more than 15%. The crosslinked P(MAA‐co‐EMA) microcapsules with DEEP and without DEEP have melting enthalpies of 67.2 and 102.9 J/g, respectively. The TGA results indicated that the thermal resistant temperature of the crosslinked microcapsules with DEEP was up to 171°C, which was higher than that of its uncrosslinked counterpart by ～20°C. The incorporation of DEEP into the microPCM increased the limiting oxygen index value of the microcapsule‐treated foams by over 5%. Thermal images showed that both microcapsule‐treated foams with and without DEEP possessed favorably temperature‐regulated properties. As a result, the microPCMs with paraffin and DEEP as core and P(MAA‐co‐EMA) as shell have good thermal energy storage and thermal regulation potentials, such as thermal‐regulated foams heat insulation materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41880.     

Interface stability behaviors of methanol‐melamine‐formaldehyde shell microPCMs/epoxy matrix composites

Microcapsules containing phase change materials (microPCMs) have been widely applied in smart temperature‐controlling materials. Interface stability plays a key role in these microPCMs/matrix composites. The aim of this study was to investigate the interface stability behaviors of methanol‐melamine‐formaldehyde (MMF) shell microPCMs containing paraffin/epoxy matrix composites. MMF prepolymer can be applied to fabricated microcapsules with smooth shells. The average diameter of the microPCMs could be controlled in the range of 5–45 μm by stirring speed of 500–6,000 r min⁻¹. From the SEM morphologies of the interphase between the microPCMs and the epoxy‐matrix, it is concluded that the interaction may be enhanced by MMF graft structure due to the increasing of molecular interaction in the interface. During a repeated heat‐transmission process, not only the repeated‐times of thermal absorbing‐releasing process will damage the interface bonding, but also higher thermal conductive speed will make the interface bearing more debonding stress. Large microPCMs in matrix may supply better interface stability. Moreover, the numerical and experimental results are consistent to obtain a clear insight into the rule of interface debonding for microPCMs/matrix composites that the interface perfection can be enhanced by increasing the thickness of interphase. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis and characterization of paraffin/TiO2‐P(MMA‐co‐BA) phase change material microcapsules for thermal energy storage

Microcapsules based on a phase changing paraffin core and modified titanium dioxide–poly(methyl methacrylate‐co‐butyl acrylate) [P(MMA‐co‐BA)] hybrid shell were prepared via a Pickering emulsion method in this study. The microcapsules exhibit an irregularly spherical morphology with the size range of 3–24 µm. The addition of BA can enhance the toughness of the brittle polymer poly(methyl methacrylate) and improve the thermal reliability of the phase change microcapsules. The ratio of BA/MMA is in the range of 0.09–0.14, and the ratio of the monomer/paraffin is varied from 0.45 to 0.60. These microcapsules exhibit a well‐defined morphology and good thermal stability. The actual core content of the microcapsules reaches 36.09%, with an encapsulation efficiency of 73.07%. Furthermore, the prepared microcapsules present the high thermal reliability for latent‐heat storage and release after 2000 thermal cycles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46447.     

Preparation and characterization of polyurethane microcapsules containing n‐octadecane with styrene‐maleic anhydride as a surfactant by interfacial polycondensation

A series of polyurethane microcapsules containing a phase change material (PCM) of n‐octadecane was successfully synthesized by an interfacial polymerization in aqueous styrene‐maleic anhydride (SMA) dispersion with diethylene triamine (DETA) as a chain extender reacting with toluene‐2,4‐diisocyanate (TDI). The average diameter of microPCMs is in the range of 5–10 μm under the stirring speed of 3000–4000 rpm. Optical and SEM morphologies of microPCMs had ensured that the shell was regularly fabricated with the influence of SMA. FTIR results confirmed that the shell material was polyurethane and the SMA chains associated on core material reacted with TDI forming a part of shell material. The shell thickness was decreasing in the range of 0.31–0.55 μm with the molar ratio of DETA/TDI from 0.84 to 1.35 and the weight of core material increasing from 40 to 80% (wt %). By controlling the weight ratio of PCM as 40, 50, 60, 70, and 80% in microPCMs, it was found using DSC that the T_m and T_c of microPCMs were in the range of 29.8–31.0^oC and 21.1–22.0°C and an obvious phase change had been achieved nearly the same temperature range of that of PCM. The results from release curves of microPCM samples prepared by 1.4, 1.7, and 2.0 g of SMA indicated the release properties were affected by the amount of the dispersant, which attributed to the emulsion effect and shell polymerization structure. The above results suggest that the shell structure of microPCMs can be controlled and the properties of microPCMs determined by shell will perform proper practical usage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4996–5006, 2006     

Improvements in the thermal conductivity and mechanical properties of phase‐change microcapsules with oxygen‐plasma‐modified multiwalled carbon nanotubes

The thermal properties and mechanical properties are the key factors of phase‐change microcapsules (microPCMs) in energy‐storage applications. In this study, microPCMs based on an n‐octadecane (C18) core and a melamine–urea–formaldehyde (MUF) shell supplemented with O₂‐plasma‐modified multiwalled carbon nanotubes (CNTs) were synthesized through in situ polymerization. Meanwhile, two different addition methods, the addition of modified CNTs into the emulsion system or into the polymer system, were compared and examined. Scanning electron microscopy micrographs showed that the microPCMs were spherical and had a broadened size distribution. Fourier transform infrared testing demonstrated that the modified CNTs did not affect C18 coated by MUF resin. The results indicate that the thermal conductivity and mechanical properties of the microPCMs were remarkably improved by the addition of a moderate amount of modified CNTs, but the heat enthalpy and encapsulated efficiency decreased slightly. Moreover, the thermal conductivity and mechanical properties of microPCMs modified with CNTs directly added to the polymer system were superior to those with CNTs added to emulsion system. In particular, when 0.2 g of modified CNTs were added to the polymer system, the thermal conductivity of the microPCMs was improved by 225%, and the breakage rates of the microPCMs at 4000 rpm for 5, 10, and 20 min decreased by 74, 72, and 60%, respectively, compared with that of the microPCMs without modified CNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45269.     

Thermal and morphological stability of polystyrene microcapsules containing phase‐change materials

Polystyrene microcapsules with paraffin wax as the active agent [phase‐change material (PCM)] were produced by a Shirasu porous glass emulsification technique and a subsequent suspension‐like polymerization process. The suitability of the obtained microcapsules for textile applications was studied. The thermal properties, surface morphology, and structural stability of the PCM microcapsules were investigated with differential scanning calorimetry, thermogravimetric analysis, and environmental scanning electron microscopy. The microcapsules could be used without any appreciable damage or irreversible changes in their integrity until 135°C. Furthermore, these microcapsules were heat‐resistant and could endure the curing conditions of textile coating up to 140°C for 30 min. In addition, the stability of the microcapsules under common laundering conditions was tested. It was confirmed that the microcapsules were durable enough and maintained their stability during stirring in hot water and alkaline solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of double‐MF shell microPCMs used in building materials

A kind of double‐shell heat energy storage microcapsule was prepared used melamine formaldehyde (MF) resin as shell material, and the properties of the microcapsules were investigated. A phase change material, with melt point of 24°C and phase transition heat of 225.5J/g, was used as core. The microcapsules would be used in indoor walls to regulate the temperature and save energy. The surface morphological structure was examined by means of scanning electron microscopy. The strength of the shell was evaluated through observing the surface change after pressure by means of scanning electron microscopy. The average diameter of the microcapsules was 5 μm ～ 10 μm. Diameter of 1 μm ～ 5 μm could also be obtained by using different stirring speeds. The globular surface was smooth and compact. The thickness was 0.5 μm ～ 1 μm. Also, the melting point of the microcapsules was 24.7°C, nearly equal to the pure phase change material. The DSC results make clear that the polymer shell of the microcapsules does not influence the properties of the phase change material. It was also found that the avoiding penetration property of the double‐shell microcapsules was better than that of single shell, and the average diameter of 5 μm was better than 1 μm. With the increase of ratio of the core material, the compactability decreased, and the shell thickness decreased. The mass ratio of core and shell was 3 : 1 to ensure that the microcapsules had good heat storage function. The measuring test showed that the microcapsules did not rupture at a pressure of 1.96 × 10⁵ Pa. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1755–1762, 2005     

相变石蜡微胶囊的制备及表征

采用分散聚合法,二乙烯苯为交联剂,制备了石蜡/P（MMA-co-MAA）相变储能微胶囊.采用光学显微镜,扫描电子显微镜（SEM）、差示扫描量热仪（DSC）和热重分析仪（TGA）对其进行表征.实验结果表明：微胶囊呈球形,平均粒径为4.2um,几乎没有粘结,其相变温度为27.24℃,相变潜热为81.53J/g,芯材含量达到72.6％,同时具有良好的热稳定性.     

聚乳酸-石蜡微胶囊相变材料的制备及表征

制备了以聚乳酸(PLA)为壁材、石蜡为芯材的相变储能微胶囊。采用红外光谱、扫描电镜、热失重分析仪和差示扫描量热仪分析了微胶囊的结构及性能。结果表明:PLA已包覆到石蜡上,该微胶囊的粒径为5~10μm;微胶囊的热稳定性能在一定范围内得到了较大程度的提高,在300℃以下无质量损失;微胶囊的储热能力高达170.52 J/g。     

窄粒径分布的液体石蜡相变微胶囊制备及性能表征

目前相变微胶囊的制备普遍采用传统的机械搅拌乳化方法,获得微胶囊的粒径大小难以控制,粒径分布范围较大。本工作采用快速膜乳化技术结合原位聚合法获得窄粒径分布的液体石蜡/密胺树脂相变微胶囊。研究发现,过膜压力和过膜次数对相变微胶囊的粒径大小和分布影响较大,当微孔玻璃膜孔径固定时,调节过膜压力和过膜次数可以控制微胶囊的粒径大小和分布。当使用孔径为10.1 μm的微孔玻璃膜时,采用过膜压力为0.2 MPa、过膜次数为4次时,可以获得粒径分布最窄的液体石蜡相变微胶囊。此时微胶囊的平均粒径为10.84 μm,相对标准偏差仅为0.16,远小于机械搅拌乳化制备的微胶囊的粒径相对标准偏差。且微胶囊表面光滑致密,无明显团聚,具有良好的耐热性能和冷/热循环稳定性,微胶囊包裹率约为80%。此外,快速膜乳化技术的引入大大提高了乳化效率,从而显著提高了微胶囊制备效率,对其他窄粒径分布的低温烷烃相变微胶囊的批量化制备具有重要意义。     

Preparation of paraffin-based phase-change microcapsules and application in geopolymer coating

A type of paraffin phase-change microcapsule for thermal insulation of exterior walls was prepared by in situ polymerization of low-softening-point paraffin (46°C) as core material and acrylic copolymer as shell. The surface morphology, phase-change thermal properties, and thermal stability were characterized by scanning electron microscopy, laser particle size distribution analysis, differential scanning calorimetry, and thermogravimetric analysis, respectively. The results showed that, for polymerization reaction temperature of 75°C and paraffin/acrylic copolymer mass ratio of 1.8, the microcapsules prepared at rotation speed of 1600 r/min with 8% emulsifiers were spherical particles with smooth surface and average particle size of 0.68 μm. The phase-change temperature and latent heat storage capacity of the microcapsules were 47.8°C and 174 J/g, respectively. The paraffin phase-change microcapsules obtained using the optimum synthesis condition were mixed in a metakaolin-based geopolymer coating at different proportions, and the thermal insulation ability of the resulting phase-change thermal energy storage coating characterized.     

用于自内冷溶液除湿的复配石蜡微胶囊的特性

以三聚氰胺?甲醛树脂为胶囊壁材、固液复配石蜡为胶囊芯材,采用原位聚合法制备了用于自内冷溶液除湿的相变材料微胶囊,研究了单一或不同类型乳化剂复配、乳化剂用量对相变材料微胶囊粒径、微观形貌及热性能的影响. 结果表明,非离子乳化剂NP-10与阴离子乳化剂SDBS复配所制微胶囊相变潜热较低,非离子乳化剂Span80和Tween80按质量比1:1复配、乳化剂占芯材质量的60%、乳化转速为1000 r/min时,所制微胶囊综合性能最佳,表面光滑致密,分散性良好,粒径均一,平均粒径为0.45 ?m,相变潜热为52.48 J/g,囊芯含量为58.44%,相变温度适用于以LiCl溶液为除湿剂的自内冷溶液除湿系统.     

溶剂挥发法制备聚砜包覆桐油自修复微胶囊

以聚砜为壁材,桐油为芯材,采用溶剂挥发法制备了聚砜（PSF）包覆桐油自修复微胶囊。考查了不同种类的分散剂、搅拌速度、芯壁比（芯材与壁材的质量比）等工艺参数对微胶囊性能的影响,通过扫描电子显微镜、光学显微镜和热重分析仪等对微胶囊的表观形貌、粒径、壁厚、包覆率和热稳定性能等进行表征。采用所合成的微胶囊制备了环氧树脂基防腐蚀涂层,并对其防腐蚀性能进行了评价。结果表明,30 ℃时,以明胶/聚乙烯醇复配体系作为分散剂,芯材与壁材质量比为1.3:1,搅拌速度为700 r/min时制备出的微胶囊表面光滑致密,粒径在130 μm左右,热稳定温度为350 ℃;盐雾实验结果表明,所制备的微胶囊自修复涂层具有良好的防腐蚀性能。     

Pickering乳液法制备复合壳层微胶囊及其在涂料中的应用

以水包油（O/W）型 Pickering乳液为模板，经 UV光聚合法制备复合壳层中空微胶囊，探究了乳化剂纳米粒子的加入方式、粒径和光敏低聚物 PUA对微胶囊壳层的影响，并将微胶囊加入到树脂涂层中，探究微胶囊作为填料对涂层基本性能的影响。使用傅立叶变换红外光谱、扫描电镜、光学显微镜、热重等仪器对微胶囊结构进行表征，并对涂层性能进行了测试。结果表明：乳化剂 SiO₂-E纳米粒子加入到油相中制备得到的中空微球表面镶嵌有 SiO₂-E纳米粒子；乳化剂纳米粒子粒径的增加，影响中空微球的形貌但对尺寸无影响；当 PUA的质量分数从 10%增加到 30%时，中空微胶囊表面分布的纳米粒子减少，断裂伸长率从 11. 1%增加至 34. 5%，而最大拉伸应力从 21. 5 MPa降低至12. 1 MPa。中空微胶囊加入到涂料中，随中空微胶囊含量的增加，涂层的铅笔硬度提高且附着力良好。     

Synthesis and properties of paraffin capsules as phase change materials

Capsules containing paraffin as phase change core were in situ synthesized by the absorption and polymerization of urea-formaldehyde prepolymer onto the core in the presence of hydrolyzed styrene-maleic anhydride copolymer as emulsifier in aqueous phase. The particle size and shell content were controlled. A series of capsules in the form of powder have been synthesized with high thermal enthalpy capacity due to the high crystallization of the core paraffin. They were stable against coalescence after heating/cooling cycles. The capsules can find potential applications such as in energy conservation, functional heat fluid and heat protection materials.     

Microencapsulated ammonium polyphosphate with boron‐modified phenolic resin

Ammonium polyphosphate (APP) was encapsulated with boron‐modified phenolic resin (BPF) by in situ polymerization with the goal of improving its hydrophobicity, thermal stability, and compatibility in polymers. The chemical and physical features of APP microcapsules were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, scanning electron microscopy, inductively coupled plasma, and laser particle sizing. The hydrophobicity was assessed by the water contact angle. The residues from thermogravimetric analyzer and muffle burner were investigated. The results showed that the APP microcapsules with BPF shell had been achieved successfully. The shell encapsulation rate mainly depended on the amount of crosslinking agent when the ratio of APP/BPF was constant. The mean particle size increased and the particle size distribution became more narrow. The hydrophobicity of APP was improved and the improvement degree mainly depended on the amount and adding rate of crosslinking agent and the conditions of heat curing. A good thermal stability and high residue char rate at high temperature were noticed for APP microcapsules. It suggests that these microcapsules might be used as an intrinsic flame retardant. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43720.     

Preparation,characterization, and prominent thermal stability of phase‐change microcapsules with phenolic resin shell and n‐hexadecane core

Microcapsules with phenolic resin (PFR) shell and n‐hexadecane (HD) core were prepared by controlled precipitation of the polymer from droplets of oil‐in‐water emulsion, followed by a heat‐curing process. The droplets of the oil phase are composed of a polymer (PFR), a good solvent (ethyl acetate), and a poor solvent (HD) for the polymer. Removal of the good solvent from the droplets leads to the formation of microcapsules with the poor solvent encapsulated by the polymer. The microstructure, morphology, and phase‐change property as well as thermal stability of the microcapsules were systematically characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimety (DSC), and thermogravimetric analysis (TGA). The phase‐change microcapsules exhibit smooth and perfect structure, and the shell thickness is a constant fraction of the capsule radius. The initial weight loss temperature of the microcapsules was determined to be 330°C in N₂ and 255°C in air, respectively, while that of the bulk HD is only about 120°C both in air and N₂ atmospheres. The weight loss mechanism of the microcapsules in different atmosphere is not the same, changing from the pyrolysis temperature of the core material in N₂ to the evaporation of core material caused by the fracture of shell material in air. The melting point of HD in microcapsules is slightly lower than that of bulk HD, and a supercooling was observed upon crystallization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

癸酸相变微胶囊的制备及热性能

以尿素、甲醛及癸酸为原料,利用原位聚合法制备了脲醛树脂包覆癸酸的相变微胶囊。以芯壁质量比、乳化剂用量、乳化转速及固化剂含量为变量设计正交实验,采用ESEM、FTIR和DSC分别表征癸酸微胶囊的微观形貌、化学结构及热性能,利用渗漏率实验测试癸酸微胶囊的防渗性能。结果表明,m(OP-10)∶m(Span-80)=4∶1的复合乳化剂有利于改善癸酸微胶囊颗粒特性。癸酸微胶囊P(芯壁质量比3∶2、乳化剂用量占芯材质量5%、乳化转速1400 r/min、固化剂间苯二酚用量占尿素质量12%)在微观形貌上分散良好且大小均一,相变潜热为123.91 J/g,渗漏率和包覆率分别为6.95%和69.7%,与癸酸微胶囊S(芯壁质量比1∶1、乳化剂用量占芯材质量6%、乳化转速1100 r/min、固化剂用量占尿素质量10%)相比,癸酸微胶囊P的渗漏率降低了57.2%,包覆率反而提高了132.3%,具有良好的热性能。     

Epoxy loaded poly(urea-formaldehyde) microcapsules via in situ polymerization designated for self-healing coatings

Self-healing systems are a next-generation technology that can offer autonomous crack repair and increase the service lifetime of a protective coating. Polymeric microcapsules containing healing agents can be used in that perspective and exhibit significant potential. In the current study, poly(urea-formaldehyde) microcapsules containing an epoxy healing agent as core material were successfully prepared using in situ polymerization. The effect of different process parameters was studied in respect to microcapsules' characteristics, that is, morphology, particle size, encapsulation efficiency and thermal properties. Spherical microcapsules with either smooth or rough surface were obtained with a size ranging from 90 to 165 μm, controlled by the stirring rate during the emulsification stage. The encapsulation efficiency varied between 65–77% with no significant dependence on the process conditions. Finally, the stability of the microcapsules during storage was investigated at different conditions.