细粒径石蜡微胶囊相变材料的制备与性能

采用阳离子和非离子复配乳化剂,通过原位聚合制备以丙烯酸酯为壁材,石蜡为芯材的细粒径微胶囊相变材料.采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、差示扫描量热(DSC)、热重(TG)及激光粒度仪分析表征了微胶囊相变材料的化学结构、表面形貌和热性能.结果表明,乳化剂的种类和壁材单体的配比对微胶囊性能有重要的影响.当采用阳离子和非离子复配乳化剂,壁材中单体甲基丙烯酸甲酯(MMA)与丙烯酸(AA)的质量比为9∶1时,微胶囊相变材料呈球形且表面光滑紧凑,尺寸仅为0.2~0.35μm,具有良好的储热能力,相变潜热高达169 J/g;微胶囊中壁材对石蜡芯材的分解具有明显热阻滞作用,分解温度比纯石蜡提高了150℃.     

丙烯酸共聚物囊壁的正十八烷微胶囊的制备和性能表征

以二丙烯酸1,4-丁二醇酯为交联剂, 成功制备了甲基丙烯酸甲酯-甲基丙烯酸共聚物为壁材, 正十八烷为囊芯的相变材料微胶囊. 采用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TG)分别考察了单体与芯材投料比、单体浓度和交联剂的含量对微胶囊形貌、相变热性能、热稳定性能的影响. 实验结果表明: 随着单体与芯材投料比或单体浓度的增加, 微胶囊表面均变得致密, 壁厚增加; 随着交联剂含量的增加, 微胶囊的表面变得更加致密光滑, 热稳定性显著增强; 随着单体与芯材投料比的增大, 微胶囊热焓值减小, 被包裹的囊芯含量减少.     

石墨烯/正十八烷微胶囊的制备与及其热性能研究

以石墨烯/正十八烷为芯材,三聚氰胺-尿素-甲醛树脂(MUF)为壁材,苯乙烯马来酸酐共聚物(SMA)为乳化剂,采用乳液聚合法制备相变微胶囊.系统研究了石墨烯对于正十八烷微胶囊性能的影响.采用场发射扫描电子显微镜(FE-SEM)、傅里叶变换红外光谱分析仪(FTIR)、拉曼光谱仪、X射线衍射仪(XRD)、Hot Disk热常数分析仪、示差扫描量热仪(DSC)和热重分析仪(TGA)对相变微胶囊的外貌形态、晶型结构和热性能进行表征和分析.结果表明,微胶囊呈圆球形且光滑,粒径约为1~30μm.当石墨烯添加量为0.1 g时,微胶囊的形貌无明显变化.当加入过量石墨烯时,微胶囊出现了明显的团聚现象.XRD测试表明,包覆于微胶囊中的石墨烯没有使微胶囊的结晶峰位置发生明显的偏移,这对于微胶囊的实际应用是有利的.微胶囊的相变热焓和包覆率随着石墨烯的加入而不断减小,但芯材的过冷现象得到了明显的改善.石墨烯对于微胶囊传热性能的提升有着显著的效果.当石墨烯的添加量为0.2 g时,微胶囊的导热系数为0.092 W·m-1·K-1,与纯微胶囊相比提高了约51%,这说明石墨烯改善了传统相变微胶囊的传热性能,提升了相变微胶囊的应用性能.     

石蜡相变微胶囊的制备与表征

采用复乳交联法制备了以相变石蜡为芯材、壳聚糖为壁材的新型储能相变微胶囊。 此相变微胶囊具有很高的相变焓值（可达110 J/g以上）,并且可以根据具体需要改变芯材的温度;TGA研究表明,该相变微胶囊具有很好的热稳定性,在150 ℃以下可以稳定存在;由于壳材料进行了化学交联反应,使得该相变微胶囊具有很好溶剂稳定性,可以在水、乙醇和乙醚等常见溶剂中稳定存在。     

十八烷/聚(St-MMA)相变微胶囊制备及表征

采用乳液聚合的方法,分别选取聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)或苯乙烯和甲基丙烯酸甲酯的共聚物为壁材,正十八烷为芯材,十二烷基苯磺酸钠(SDBS)为乳化剂,制作相变储能微胶囊。用粒径分析仪、透射电子显微镜(TEM)、热重分析仪(TG)和示差扫描量热测试仪(DSC)对微胶囊的形貌、相变热性能和热稳定性分别进行表征。结果表明:壁材选取两者共聚物,当两种单体的比例为St∶MMA=1∶5,SDBS用量为1.5g(总质量的3%)时,微胶囊粒径大小均匀,粒子分散性好,壁材的包裹性好。微胶囊的放热峰为起始温度为27.3℃,终止温度为31.9℃,相变温度为28.9℃,相变焓为48.4J/g。TG表明长期使用温度不能超过131℃。IR分析微胶囊中含有芯材和壁材。这种十八烷/聚(St-MMA)相变微胶囊可以用于诸能材料。     

纳米二氧化硅改性石蜡微胶囊相变储能材料的研究

以石蜡为芯材,甲基丙烯酸甲酯-丙烯酸共聚物为壁材,纳米SiO2为改性剂,采用原位聚合法制备了石蜡微胶囊相变储能材料,系统研究了添加纳米SiO2对石蜡微胶囊相变材料性能的影响;采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、示差扫描量热法(DSC)和热重分析(TGA)等对石蜡微胶囊相变材料的化学结构、表面形貌和热性能进行了表征.研究表明,纳米SiO2能够有效提高微胶囊壁材的热稳定性,当丙烯酸酯壁材中添加3％改性纳米SiO2时,微胶囊呈球形且表面光滑,尺寸250 ～ 300 nm,具有良好的储热能力,相变潜热高达134.79 J/g,分解温度比未添加改性纳米SiO2的石蜡微胶囊提高了40 K,经过1000次热循环测试,石蜡渗漏率仅2.96％.     

乳化工艺对微胶囊型硬脂酸相变材料热性质的影响

以硬脂酸为芯材, 碳酸钙为壁材, 采用原位聚合法制备了微胶囊型相变材料; 通过扫描电子显微镜、 红外光谱及差热-热重分析对其表面形貌和热性质进行了表征; 通过改变乳化剂的种类及用量, 研究了乳化工艺对微胶囊型相变材料表面形貌、 相变温度和包覆率的影响. 实验结果表明, 在选用的3种乳化剂十二烷基苯磺酸钠、 十六烷基三甲基溴化铵和曲拉通X-100中, 十二烷基苯磺酸钠相对效果最好, 乳化剂与芯材最佳质量比为0.5%, 相变温度为112.24 ℃时, 封装率达到92.1%.     

具有薄荷香味的相变微胶囊的制备与表征

利用界面聚合法,以异佛尔酮二异氰酸酯与己二胺为单体聚合形成的聚脲为外壳,以正十八烷、薄荷素油的混合物为芯材,制备了具有薄荷香味的相变微胶囊。利用光学显微镜、扫描电镜、红外光谱仪、差示扫描量热仪、热重分析仪等对微胶囊的形貌、化学结构和热性能进行了表征。结果表明:制备的微胶囊为球形,平均粒径约7.0μm,有较高的储热能力和较好的热稳定性;芯材中添加8.3%的正十四醇或高熔点石蜡,可很好地抑制相变微胶囊的过冷现象。     

一种致密的相变储能微胶囊的制备与表征

制备了以聚脲为第一壁材、苯乙烯-二乙烯苯为第二壁材,以相变点在16℃左右的石蜡为芯材的相变储能微胶囊。采用红外光谱、差示扫描量热分析、热重分析测试技术表征了制备的相变储能微胶囊的结构组成以及热性能;采用溶剂淋洗法研究了影响包覆率的因素。结果表明,相变储热微胶囊是复合相变材料,微胶囊的热稳定性好,致密性优良;通过对水油比、乳化剂及苯乙烯-二乙烯苯用量等各因素对微胶囊包覆率影响的讨论,得出在水与油质量比3.2,乳化剂相对于水的质量分数为2%时,加入苯乙烯与二乙烯苯质量比为10∶1混合液的质量分数为6.0%时,其包覆率达81.14%;制备的微胶囊能耐较高温度,在150℃以下无质量损失,且微胶囊储热能力高达80J/g。同时发现,储热能力与芯壁比有关,比值越大储热潜能越高。     

界面聚合法制备正二十烷微胶囊化相变储热材料

用界面聚合的方法,以甲苯-2,4-二异氰酸酯(TDI)和己二胺(HDA)为反应单体,非离子表面活性剂聚乙二醇壬基苯基醚(OP)为乳化剂,合成了正二十烷为相变材料的聚脲包覆微胶囊. 结果表明,二异氰酸酯和己二胺按质量比为1.5∶ 0.8进行反应. 空心微胶囊的直径约为0.2 μm,含正二十烷微胶囊直径为2~6 μm. 红外光谱分析证明, 囊壁聚脲是由TDI及HDA 2种单体形成. 正二十烷包裹效率为65%~80%. 微胶囊的熔点接近囊芯正二十烷的熔点,而其储热量在壁材固定时随囊芯的量而变. 热重分析结果表明,囊芯正二十烷、含正二十烷的微胶囊以及壁材聚脲,能够耐受的温度分别约为130、165及250 ℃.     

Microwave-assisted synthesis of poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules

In this study, lauryl alcohol suitable for thermal energy storage applications was microencapsulated in a poly(urea-formaldehyde) shell. The microcapsules were prepared by microwave-assisted in situ polymerization. The morphology and particle size of the poly(urea-formaldehyde)/lauryl alcohol phase change energy storage microcapsules(UF/LA PCESMs) were analyzed using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering. The latent heat storage capacities of lauryl alcohol and UF/LA PCESMs were determined using differential scanning calorimetry. The chemical composition of the microcapsules was characterized using Fourier transform infrared spectroscopy. All of the results show that UF/LA PCESMs were synthesized successfully and that the latent heat storage capacity and encapsulation efficiency were 156.0 J/g and 75.0%, respectively, and the diameter of each microcapsule was around 150 nm.     

Preparation and Performance of Dual-functional Magnetic Phase-change Microcapsules

The fabrication of desired anti-magnetic materials for irradiation shielding remains a challenge to date. In this work, a new type of dual-functional magnetic shielding phase change microcapsules with paraffin as the core, melamine-formaldehyde (MF) resin as the shell and doped with magnetic particles in the shell were successfully prepared by in situ polymerization. The magnetic particles were dispersed in the shell layer by coating a hydrophilic emulsifier on the surface. These microcapsules were specifically applied to the field of magnetic shielding by the screen printing method. The effect of magnetic particles on the performance of phase-change microcapsules was examined by differential scanning calorimetry and thermogravimetric analyses. The magnetic type and magnetic strength of the microcapsules were studied by the vibrating sample magnetometer. Moreover, the effects of different magnetic particles (Fe₃O₄, CrO₂) on the performance of phase change microcapsules and the magnetic strength of microcapsules were compared. The results showed that these two kinds of magnetic particles can greatly improve the phase change latent heat, thermal stability, and thermal conductivity of the microcapsules. Finally, the great magnetic shielding role of these microcapsules was demonstrated in both static and pulsed magnetic fields through the screen printing of magnetic shielding ink on wallpaper. Incorporating 0.5 g Fe₃O₄ inside of microcapsules, specifically, the magnetic intensity was effectively reduced by ∼250 Oe within a short distance in the static field. We expect that these magnetic microcapsules hold great potential for the shielding of irradiations via the screen printing on various substrates.     

PW based phase change nanocomposites containing <Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Phase change nanocomposites were prepared by dispersing γ-Al₂O₃ nanoparticles into melting paraffin wax (PW). Intensive sonication was used to make well dispersed and homogeneous composites. Differential scanning calorimetric (DSC) and transient short-hot-wire (SHW) method were employed to measure the thermal properties of the composites. The composites decreased the latent heat thermal energy storage capacity, L _s, and melting point, T _m, compared with those of the PW. Interestingly, the composites with low mass fraction of the nanoparticles, have higher latent heat capacity than the calculated latent heat capacity value. The thermal conductivity of the nanocomposites was enhanced and increased with the mass fraction of Al₂O₃ in both liquid state and solid state.     

Dispersing different nanoparticles in paraffin wax as enhanced phase change materials

Highly conductive nanoparticles were proposed to be dispersed into phase change materials (PCMs) such as paraffin wax for heat transfer enhancement. The mixture, often referred to as nanoparticle-enhanced phase change material (NePCM), has been studied extensively for latent heat energy storage but with conflicting results. This study attempts to understand this problem by investigating the stability of NePCMs under multiple thermal (melting–solidification) cycles, which has not been well explained in previous studies. We believe that stability of a NePCM is prerequisite for any experimental investigation of its thermal properties or application. In this study, paraffin wax was chosen as the base material. Three different types of nanoparticles were tested, i.e., multi-walled carbon nanotubes, graphene nanoplatelets, and aluminum oxide nanoparticles (Al₂O₃). The nanoparticles were dispersed into paraffin wax at varying mass fractions using mechanical dispersion methods (sonication, stirring) with and without different surfactants. Stability of different mixtures was investigated after consecutive thermal cycles performed in an environmental chamber. Significant coagulation and deposition of nanoparticles were found after a few thermal cycles regardless of the nanoparticle type, concentration, or dispersion method. Different boundary conditions in heating were also examined for their effects. None of these methods led to long-term stable NePCMs. The “negative” results from this study indicate that long-term stability of NePCM (at least for the paraffin wax and nanoparticles tested) remains a major challenge and requires further research with a multidisciplinary approach.

     

Microencapsulation of bisphenol-A bis (diphenyl phosphate) and influence of particle loading on thermal and fire properties of polypropylene and polyethylene terephtalate

Microencapsulated flame retardant, bisphenol-A bis (diphenyl phosphate) (BDP), with a silane shell was prepared by sol–gel process with the goal of incorporating them in polymeric matrices by melt blending to improve the flame retardancy of isotactic polypropylene (iPP) and polyethylene terephtalate (PET). The influence of the loading content on thermal transitions has been studied by differential scanning calorimetry (DSC), the thermal stability of the polymer/microcapsules composites has been assessed by thermogravimetric analysis (TGA) and cone calorimetry has been used to study the fire reaction. It was noticed that the microcapsules have a limited influence on the thermal transitions of iPP matrix, but a decrease of the melting and glass transition temperatures was detected for the PET microcomposites. TGA results showed that the addition of microcapsules could improve char formation of the PET systems both in nitrogen and in air atmospheres, whereas only a small improvement of the thermal stability was detected in oxidative atmosphere for the iPP samples. Furthermore, cone calorimeter experiments show that the incorporation of microcapsules in the iPP gives almost no improvement in the iPP fire reaction. However, the microcapsules act as flame retardant in PET reducing the heat release rate during the combustion and the total heat evolved. Therefore, microcapsules can act as a char promoter agent to enhance the fire resistance in the case of PET.     

正十六烷聚脲微胶囊化相变材料

用界面聚合法，合成了直径大约2.5 μm可用于热能储存含相变材料的聚脲包覆微胶囊.在含乳化剂的水溶液中，将溶有芯材正十六烷的有机相乳化成微米级油性液滴，随后加入的水溶性单体二胺与甲苯2,4-二异氰酸酯在胶束界面相互反应形成囊壁.分别用乙烯二胺，1,6-己二胺和它们的混合物作为水溶性单体进行了研究.并用红外光谱和热分析分别考察了不同胺类对微胶囊化学结构和热性质的影响.红外谱图显示合成了聚脲微胶囊，热重曲线表明含正十六烷的聚脲微胶囊能够耐受大约300 ℃高温，差示扫描量热测试表明所有样品均具有合适的相转变热，冷热循环实验揭示微胶囊能够维持储热容量不衰减.研究表明微胶囊化的正十六烷作为相变储热材料具有良好的应用前景.     

硬脂酸丁酯微胶囊的制备与表征

采用原位聚合法用脲醛树脂包覆硬脂酸丁酯,制得相变储热微胶囊.利用激光粒径分布仪、扫描电镜、差示扫描量热仪(DSC)和傅立叶转换红外光谱仪分别研究了微胶囊的粒径分布、表面形态、热性能和壳结构.结果表明,所得微胶囊粒径分布均匀,表面光洁,具有良好的韧性和致密性.不同的制备工艺对微胶囊粒径分布有一定的影响,其中在28 000 r/m in下乳化5 m in时,所得微胶囊的粒径分布集中在1~4μm.DSC测定结果显示硬脂酸丁酯微胶囊的最大相变焓为68 J/g.     

潜伏性热释放型微胶囊固化剂2苯基咪唑-聚甲基丙烯酸缩水甘油酯的结构表征与性能研究

以2-苯基咪唑(2PZ)为芯材,聚甲基丙烯酸缩水甘油酯(PGMA)为壁材,采用溶剂挥发技术,成功地制备了一种新型潜伏性热释放型微胶囊固化剂2PZ-PGMA。通过FT-IR、TGA、SEM、粒度分析和DSC对微胶囊固化剂的化学结构、芯材含量、表面形貌、粒径分布及固化性能等进行了表征。所制备的微胶囊固化剂表面光滑,粒径分布较窄,平均粒径为约17.6μm,壁材厚度为约1.1μm,芯材2PZ含量为20.1(wt)%。由微胶囊固化剂与环氧树脂E-51制备的单组分胶粘剂,具有优良的固化特性、潜伏性能和粘接性能,可在100℃下30min内实现固化,室温储存期达33d以上,拉伸剪切强度达15.36MPa。     

A novel form-stable paraffin-based hydroxyl-terminated polybutadiene binder containing microencapsulated paraffin wax

Leakage and incompatibility of paraffin wax (PW) in hydroxyl-terminated polybutadiene (HTPB) binders is a major obstacle to its application in polymer-bonded explosives (PBX). In order to solve this issue, we designed a microencapsulated PW (MePW)/PW/HTPB composite in this paper. Melamine–formaldehyde-shelled MePW (MF MePW)/PW/HTPB composites with different contents of MePW and PW were prepared by cast molding method. The chemical composition, crystallinity and microstructure of MePW/PW/HTPB composites were analyzed with Fourier transformed infrared spectroscopy, X-ray diffraction and scanning electron microscope, respectively. The results showed that PW and MF MePW have been uniformly dispersed in HTPB without any chemical interaction. Moreover, differential scanning calorimeter analysis, thermal gravimetric analyzer, thermal cycling test, leaking test, tensile and compressive test were used to investigate the thermal and mechanical properties of these composites. The composites have high latent heat and good thermal reliability. The thermal stability, tensile and compressive strength of MePW/PW/HTPB composites were dramatically increased with the increasing mass fraction of MePW. The introduction of MePW can obviously prevent the leakage of PW in both HTPB binders and PBX. Consequently, it is anticipated that MePW can be used in the next-generation of paraffin-based high-temperature PBX systems.