石蜡基微胶囊相变材料研究进展北大核心CSCD

本文从微胶囊壁材出发,重点介绍了石蜡基/高分子、无机和高分子-无机杂化壳微胶囊的制备及应用,并总结了上述微胶囊的优势和不足。其中石蜡基/高分子壳微胶囊的壁材包括三聚氰胺-甲醛树脂、脲醛树脂、三聚氰胺-甲醛-尿素树脂、聚氨酯树脂、丙烯酸树脂等,石蜡基/无机壳微胶囊的壁材包括二氧化硅、二氧化钛、碳酸钙、氧化锌等,石蜡基/高分子-无机杂化壳的壁材包括三聚氰胺-甲醛树脂、三聚氰胺-甲醛-尿素树脂、丙烯酸树脂等与二氧化钛、二氧化硅等无机粒子复合。并对石蜡基微胶囊相变材料的未来发展方向和应用前景进行展望,以期为今后研究提供借鉴。     

甲胺基阿维菌素苯甲酸盐微胶囊的制备与表征

以三聚氰胺-甲醛树脂为壁材,采用原位聚合法制备了甲胺基阿维菌素苯甲酸盐微胶囊,研究了三聚氰胺与甲醛的质量比、芯壁比、乳化剂、搅拌速度与时间、pH值、温度等因素对微胶囊形成的影响,对制备的微胶囊进行了表征,测定了甲维盐微胶囊化前后的光解率。结果表明,三聚氰胺与甲醛质量比为1∶2、芯材与壁材质量比为3∶2、以质量分数1%羟乙基纤维素(HEC)为乳化剂、在1000r/min搅拌速度下、pH=5.0和50℃保温2h可制备出形貌较好、平均粒径4.4μm的甲维盐微胶囊。红外光谱分析证明,甲维盐已完全被包覆在微胶囊中。紫外分光光度法测定其缓释性能良好。光解实验表明,微胶囊化可有效降低甲维盐原药的光解。     

光致变色微胶囊的制备与性能

以蜜胺树脂为壁材、光致变色材料为芯材,采用原位聚合法制备了具有光致变色性能的微胶囊.研究了三聚氰胺/甲醛摩尔比、壁材与芯材的用量比、乳化剂浓度等因素对微胶囊形貌及性能的影响.在最佳工艺条件下制备的变色微胶囊,在日光和紫外光下具有快速、可逆的光致变色性能.     

界面聚合法制备正二十烷微胶囊化相变储热材料

采用界面聚合的方法, 以甲苯鄄2,4-二异氰酸酯(TDI)和乙二胺(EDA)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, 二异氰酸酯和乙二胺按质量比1.9:1 进行反应. 以透射电镜和激光粒度分析仪分析微胶囊, 测得空心微胶囊直径约为0.2 μm, 含正二十烷微胶囊约为2-6 μm. 红外光谱分析证明, 壁材料聚脲是由TDI 及EDA 两种单体形成的. 正二十烷的包裹效率约为75%. 微胶囊的熔点接近囊芯二十烷的熔点, 而其储热量在壁材固定时随囊芯的量而变. 热重分析表明, 囊芯正二十烷、含正二十烷的微胶囊以及壁材料聚脲, 能够耐受的温度分别约为130 ℃、170 ℃及270 ℃.     

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 ℃.     

微胶囊填充型自修复聚合物及其复合材料

微胶囊填充型自修复聚合物及其复合材料是近年来高分子科学界的研究热点之一。本文介绍了含有微胶囊聚合物复合材料自修复的概念和机理,综述了近5年来针对不同基体材料的微胶囊自修复研究情况,包括环氧树脂、乙烯基酯树脂、纤维增强环氧树脂复合材料、弹性体以及聚甲基丙烯酸甲酯等基体材料。本文同时介绍了微胶囊的芯材和壁材、微胶囊的粒径、修复时间和压强等因素对复合材料自修复性能的影响,以及自修复效果的评价方法。最后对微胶囊填充型自修复聚合物及其复合材料的研究前景进行了展望。     

相变调温微胶囊的制备

采用原位聚合法用三聚氰胺-甲醛树脂包覆正十八烷,制备出相变微胶囊．利用扫描电镜和差示扫描量热仪对微胶囊试样的表面形貌和热物理性能进行了研究．实验结果表明：制备的相变微胶囊表面光滑,平均粒径2．84μm,平均壁厚0．41μm．     

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。     

纳米木质素/二氧化硅基微胶囊的制备及在自愈合涂层中的应用

利用磷酸化改性木质素/二氧化硅复合纳米颗粒(PAL/SiO₂)作为壁材包埋活性组分异佛尔酮二异氰酸酯(IPDI)制备微胶囊(PAL/SiO₂-IPDI). 通过加入少量反应活性更高的聚合多甲基多二异氰酸酯(PMDI), 与水反应形成聚脲, 以增加微胶囊的壁厚. 采用光学显微镜、 扫描电子显微镜(SEM)和激光粒度分析仪(DLS)研究了PAL/SiO₂复合纳米粒子掺杂量, 水油比和剪切速率对微胶囊表面形貌、 粒径和壁厚的影响. 结果表明, 所制备的微胶囊呈现规整球形, 壁厚为2.36~3.50 μm, 平均粒径为40.3~201.5 μm. IPDI作为芯材包埋在微胶囊中, 芯材含量约为82.8%. 将制备的PAL/SiO₂-IPDI微胶囊添加到环氧树脂中得到自愈合环氧树脂涂层. 其在高盐浓度溶液中的抗侵蚀测试结果显示, 添加质量分数4%的PAL/SiO₂-IPDI微胶囊的环氧树脂涂层在划破后能够快速愈合, 显著降低基底的腐蚀电流和腐蚀速率. 纳米压痕实验表明, 环氧涂层的硬度为249.99 MPa, 而添加PAL/SiO₂-IPDI微胶囊后硬度增加到302.98 MPa, 弹性模量也有提高.     

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.     

The Potential of Microencapsulated Self-healing Materials for Microcracks Recovery in Self-healing Composite Systems: A Review

The autonomic self-healing materials based on microcapsules have made major advancements for the repairing of microcracks in polymers and polymer composite systems. Self-healing encapsulated materials have the inborn ability to heal polymeric composites after being damaged by chemical and mechanical progressions. These intelligent micro-encapsulated self-healing materials possess great capabilities for recovering the mechanical as well aesthetic properties and barrier properties of the polymeric structures. Based on real world observations and experimental data, it is believed that microcracks and microcracking in polymeric materials can result because of many chemical and physical routes and is one of the foremost critical issues for polymeric materials. Especially in polymeric coatings, these microcracks can lead towards disastrous failure, and conventional healing systems like patching and welding cannot be used to repair microcracks at such a micro-level. Self-healing materials, especially, capsule based self-healing materials is a new field sought as an alternative to the conventional repairing techniques, requiring no manual intrusion and uncovering. This review covers the basic and major aspects of the microencapsulated self-healing approach like the effect of synthesis parameters on the size of microcapsules, healing efficiency determination, and the potential of the existing developed microencapsulated agents.     

Micromechanical assessment of PMMA microcapsules containing epoxy and mercaptan as self-healing agents

Mechanical properties of microcapsule shell have great influence on microcapsule suitability as a mechanical trigger in a self-healing composite. The elastic modulus and hardness of polymethyl methacrylate (PMMA) microcapsules containing epoxy prepolymer (EC 157) and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) as healing agents were investigated using nanoindentation technique. The influence of the PMMA average molecular weight (M_W), the kind of core material, and the mechanical mixing rate on the mechanical properties of the microcapsule shell were studied using the Taguchi experimental design approach. The results indicated that the most important factors which affect the elastic modulus and the hardness of microcapsules shell are the Mw of PMMA and the kind of core material. The average elastic modulus of PMMA shell of epoxy and mercaptan-loaded microcapsules was found between 2.386 and 3.495 GPa. The hardness of PMMA shell of healing agent microcapsules was obtained in the range of 0.064–0.219 GPa. This constitutes essential knowledge in order to design capsules with tailored properties for self-healing materials.     

Preparation of hybrid microcapsules and application to self‐healing agent

It was tried to prepare hybrid microcapsules composed of porous inorganic particles and epoxy resin shell and to apply to the self‐healing agent. A water soluble imidazole of gelation promoting agent as the core material was microencapsulated in the porous inorganic particles, which were coated with epoxy resin. The porous inorganic particles were prepared with the interfacial reaction between sodium silicate and calcium ion in the (W/O) dispersion. In the experiment, the concentration of sodium silicate and the mixing speed to form the (W/O) dispersion were mainly changed. The porous inorganic particles were immersed in the aqueous solution dissolving imidazole and then, added in the corn oil dissolving epoxy resin to be microencapsulated with gelated epoxy resin. The hybrid microcapsules containing imidazole with the mean diameters from 200 to 400 µm were able to be prepared and to induce the gelation reaction of epoxy resin by breaking the hybrid microcapsule shell due to heating. Copyright © 2013 John Wiley & Sons, Ltd.     

Efficient Entrapment of Oxirane Ring Containing Compounds in Thermally Stable Poly(urea-formaldehyde) Polymer Shell Wall

This article aims to address the problems associated with the encapsulation of oxirane ring containing compounds in poly(urea-formaldehyde) (PUF) shell for application in self-healing composite systems. The main objectives were to produce non-agglomerated, stable microcapsules, and to control the pH drop during the encapsulation via oil-in-water emulsion polymerization. In the modified method; two stage additions of urea and formaldehyde monomers, core to shell ratio, weight percent and combination of two surfactants/emulsifiers were altered to produce the desired product. Analysis was done with optical microscope (OM), scanning electron microscopy (SEM), FTIR, particle size analyzer, and thermogravimetric analysis (TGA). The pH drop was confirmed by using a common epoxy resin, an epoxy functionalized polydimethylsiloxane (E-PDMS), and epoxidized palm oil (EPO) as cores. The modified oil-in-water emulsion polymerization of PUF was effective in preventing the pH drop during the encapsulation and a product stable for more than 3 months with less agglomeration was produced. The method produced microcapsules having diameters less than 100 μm at lower agitation rates. The modified method is only applicable to epoxy resin and not for compounds like amine hardeners. The use of stable microcapsules in self-healing coatings can lead towards cost reduction implied for repair and maintenance purposes.     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.     

Microencapsulation of styrene with melamine-formaldehyde resin

Melamine-formaldehyde (MF) resin-walled microcapsules containing styrene were prepared by in situ polymerization in an oil-in-water emulsion. In response to the characteristics of styrene (i.e., high volatility, non-polarity, low molecular weight, and low viscosity), the synthesis method was improved by optimizing the reaction conditions accordingly. It was found that utilization of macromolecular emulsifier of lower molecular weight, moderate dispersion rate, and higher feeding weight ratio of core/shell monomers is critical for the fast formation of capsules’ wall. The highest loading of styrene in the resultant microcapsules can be about 60%, and mean diameter of the capsules fell in the range of 20∼71 μm, which can be adjusted by changing processing parameters. It is believed that the present work provides a feasible approach to encapsulate monomers for manufacturing polyester based self-healing composites.     

Smart Coating Based on Urea-Formaldehyde Microcapsules Loaded with Benzotriazole for Corrosion Protection of Mild Steel in 3.5 % NaCl

Urea-formaldehyde (UF) microcapsules loaded with linseed oil (LO) and benzotriazole (BTA) as core materials have been synthesized by in situ emulsion polymerization. The capsules were characterized by FTIR spectroscopy and particle size analysis. Surface morphology of the microcapsules was analyzed using scanning electron microscopy (SEM). The microcapsules were incorporated into epoxy resin and coated on a mild steel substrate to form a corrosion resistant organic coating. The self-healing property of coatings loaded with different weight % of microcapsules containing LO + BTA was tested by immersion of the UF coated mild steel specimens in 3.5 wt % NaCl solution. It was analyzed through visual inspection, weight loss measurements, and SEM of the scribed region of coating. It was observed that the addition of microcapsules enhances the corrosion resistance of the scratched samples.

     

Preparation of monodisperse crosslinked polymelamine microcapsules by phase separation method

Monodisperse polymelamine microcapsules were prepared by phase separation method. Control of microcapsule diameter was investigated using the uniform-sized oil-in-water emulsion droplets as the capsule core. The monodisperse emulsion droplets were prepared using the Shirasu porous glass (SPG) membrane emulsification technique. The effects of the diameter of the oil droplet and concentration of sodium dodecyl sulfate (SDS), which is a typical emulsifier in SPG membrane emulsification, on microencapsulation were investigated. The microcapsules were aggregated when oil droplets with small size were microencapsulated at high SDS concentration. To reduce the SDS concentration, the creamed emulsion was used. The monodisperse polymelamine microcapsules were successfully prepared by using the creamed emulsion. The microcapsule diameter was almost similar to the diameter of the encapsulated oil droplet. The coefficient of variation values was about 10% for all microcapsules prepared in this study. Control of microcapsule diameter was achieved in the range of 5–60 μm.     

Responsive core-shell latex particles as colloidosome microcapsule membranes

Responsive core-shell latex particles are used to prepare colloidosome microcapsules using thermal annealing and internal cross linking of the shell, allowing the production of the microcapsules at high concentrations. The core-shell particles are composed of a polystyrene core and a shell of poly[2-(dimethylamino)ethyl methacrylate]-b-poly[methyl methacrylate] (PDMA-b-PMMA) chains adsorbed onto the core surface, providing steric stabilization. The PDMA component of the adsorbed polymer shell confers thermally responsive and pH-responsive characteristics to the latex particle, and it also provides glass transitions at temperatures lower than those of the core and reactive amine groups. These features facilitate the formation of stable Pickering emulsion droplets and the immobilization of the latex particle monolayer on these droplets to form colloidosome microcapsules. The immobilization is achieved through thermal annealing or cross linking of the shell under mild conditions feasible for large-scale economic production. We demonstrate here that it is possible to anneal the particle monolayer on the emulsion drop surface at 75-86 °C by using the lower glass-transition temperature of the shell compared to that of the polystyrene cores (～108 °C). The colloidosome microcapsules that are formed have a rigid membrane basically composed of a densely packed monolayer of particles. Chemical cross linking has also been successfully achieved by confining a cross linker within the disperse droplet. This approach leads to the formation of single-layered stimulus-responsive soft colloidosome membranes and provides the advantage of working at very high emulsion concentrations because interdroplet cross linking is thus avoided. The porosity and mechanical strength of the microcapsules are also discussed here in terms of the observed structure of the latex particle monolayers forming the capsule membrane.