石蜡/聚脲相变微胶囊的制备及表征

以固体石蜡和液体石蜡熔融混合进行复配,复合石蜡的相变温度和相变焓都随固体石蜡含量的增加而升高,以固液比3∶7制备的复合石蜡熔点为28.3℃,相变潜热为100.04kJ/kg。以此复合石蜡作为微胶囊的芯材,以甲苯2,4二异氰酸酯(TDI)和乙二胺为单体,OP-10为乳化剂,采用界面聚合法在复合石蜡表面包覆聚脲囊壁材料制备石蜡/聚脲相变微胶囊,用扫描电镜(SEM)观察了乳化搅拌速度和反应温度对相变微胶囊表面形貌的影响,并用红外光谱(FTIR)、热重(TG)和差示扫描量热法(DSC)对相变微胶囊进行了表征。实验结果表明:在乳化搅拌速度2000r/min、反应温度70℃时制备的石蜡/聚脲相变微胶囊颗粒呈球形分布,平均粒径在3~4μm范围内,分散均匀,颗粒表面光滑、致密,熔点为28.1℃,相变潜热为58.4kJ/kg,包覆效率为87.5%。     

丙三醇改性聚脲微胶囊相变材料的研制与性能

以硬脂酸丁酯为芯材,苯乙烯马来酸酐共聚物(SMA)为乳化分散剂,以单体2,4-甲苯二异氰酸酯(TDI)和二亚乙基三胺(EDTA)反应并采用丙三醇进行改性形成的聚脲树脂为壳体,采用界面聚合制备微胶囊相变材料。采用差示扫描量热仪(DSC)、扫描电镜(SEM)、光学显微镜等分别对微胶囊的热性能、表面形态进行研究和分析。所制备微胶囊表面光滑致密,相变温度24.2℃,相变热90 J/g。对微胶囊的致密性和稳定性研究结果表明,所制备丙三醇改性微胶囊的致密性和稳定性,如耐乙醇洗涤稳定性和耐热稳定性均比传统的未改性微胶囊有很大程度的提高。     

乳液模板法制备新型pH响应微胶囊材料的研究

利用乳液模板法制备了新型微胶囊材料。以小麦水解蛋白为稳定剂，水为外相、辛癸酸甘油酯为内相，制备了水包油型Pickering乳液。通过显微镜和粒径统计表征了乳液的微观结构，稳定剂质量分数为1%、2%、3%、4%和5%的Pickering乳液平均液滴直径分别为96.8μm、78.2μm、62.31μm、47.6μm和38.7μm。加入戊二醛与蛋白的氨基发生席夫碱反应，交联界面相形成微胶囊，通过红外光谱、显微镜和EDS Mapping证实了微胶囊的形成。戊二醛浓度为5%、10%、20%、30%、40%和50%时，微胶囊产率分别为75.9%、52.9%、35.3%、41.7%、39.0%和38.2%。由于席夫碱的亚胺基团具有pH响应性，可在酸性条件下断裂，故而该微胶囊具有pH响应性，能够在1mol/L盐酸环境下发生结构破裂，达到控制释放内部包封的油溶性组分的目的。     

界面聚合聚脲/聚氨酯双层微胶囊相变材料的研制与性能

以硬脂酸丁酯为芯材,苯乙烯马来酸酐共聚物(SMA)为乳化分散剂,采用界面聚合制备双层微胶囊相变材料,其外壳体为甲苯-2,4-二异氰酸酯(TDI)和二乙烯三胺(DETA)反应形成的聚脲壳层,内壳体为TDI与聚丙二醇2000(PPG2000)反应形成的聚氨酯壳层。采用差示扫描量热仪(DSC)、热重分析仪(TGA)、扫描电镜(SEM)、光学显微镜等分别对微胶囊的热性能、表面形态做了研究和分析。结果表明,所制备的双层微胶囊表面光滑致密,相变温度24.1℃,相变热85 J/g。所制备双层微胶囊的致密性和耐热稳定性均比单层微胶囊有很大程度的提高。     

制备过程参数对石蜡-聚脲相变微胶囊性能的影响

以质量比为3:7的固体石蜡和液体石蜡制备的复合石蜡为微胶囊的芯材,以甲苯-2,4-二异氰酸酯和乙二胺为单体,辛基酚聚氧乙烯醚为乳化剂,采用界面聚合法在复合石蜡表面包覆聚脲制备石蜡-聚脲相变微胶囊,探讨乳化转速、乳化剂用量和聚合反应温度对石蜡-聚脲相变微胶囊粒径、包覆效率及蓄热性能的影响。结果表明,在乳化转速为2000r/min,乳化剂与复合石蜡的质量比为0.06,反应温度为70℃的条件下制备的石蜡-聚脲相变微胶囊的平均粒径为3~4μm,熔点为28.1℃,相变潜热为58.4 k J/kg,包覆效率为87.5%。     

芯材表面修饰法制备聚脲石蜡相变微胶囊及其表征

采用芯材表面修饰法制备了聚脲石蜡相变微胶囊。首先在固体石蜡颗粒表面引入氨基(-NH2),制备表面氨基修饰的固体石蜡芯材,再加入2,4-甲苯二异氰酸酯(TDI)和改性胺固化剂,形成聚脲壁包覆芯材。用差示扫描量热仪、傅里叶红外光谱仪(FT-IR)和激光粒径分布仪表征了芯壁用量比以及搅拌速度对相变微胶囊结构和性能的影响。FT-IR测试结果表明,该方法成功地在固体石蜡微球的表面引入了氨基。固定转速时,随着芯壁用量比中TDI用量的增加,微胶囊相变潜热明显增加;在十八胺与TDI摩尔比相同的条件下,随着芯材制备搅拌速率的增大,微胶囊的平均粒径减小而相变潜热明显增加。当搅拌速率为800 r/min,十八胺与TDI摩尔比为1∶2时,所制备的聚脲石蜡相变微胶囊包覆完整,热稳定性好,平均粒径为18.262μm,相变潜热可达142.8 J/g,包覆率达63%以上。     

芯材制备条件对聚脲石蜡相变微胶囊性能的影响

采用吐温-80(Tween-80)和司班-80(Span-80)复配乳化剂,通过芯材表面修饰法制备以聚脲为壁材,石蜡为芯材的石蜡相变微胶囊材料。采用差示扫描量热仪、激光粒径分布仪和扫面电子显微镜对石蜡相变微胶囊进行了形貌表征和性能分析。通过对石蜡相变微胶囊芯材制备的单因素试验,对聚脲石蜡相变微胶囊的性能进行了研究。实验结果表明,复配乳化剂的使用能使芯材乳液的稳定性增加,而复合乳化剂用量、搅拌速率和乳化时间的延长有利于芯材乳液的稳定性的增加;芯材制备过程中,搅拌分散转速、搅拌分散时间及搅拌降温速率对石蜡相变微胶囊的性能有重要影响。     

核壳质量比对石蜡-聚脲相变微胶囊性能的影响

以质量比为3∶7的固体石蜡与液体石蜡均匀混合得到复合石蜡,甲苯-2,4-二异氰酸酯(TDI)单体和乙二胺(EDA)在乳化剂辛基酚聚氧乙烯醚的乳化作用下,通过界面聚合包覆在芯材复合石蜡的表面形成石蜡-聚脲相变微胶囊,对比差热曲线和加热-冷却曲线表征芯材复合石蜡的蓄热性能,探讨EDA与TDI质量比对聚脲囊壁产量的影响,以及核壳质量比对石蜡-聚脲相变微胶囊粒径、包覆效率以及蓄热性能的影响。结果表明:加热-冷却曲线与差示扫描量热曲线显示复合石蜡的熔点接近;聚脲囊壁的产量随着水合EDA与TDI质量比的增大近似线性增大,质量比达到0.5∶1.0后,聚脲囊壁的产量不再增大;核壳质量比为2.0∶1.0时制得石蜡-聚脲相变微胶囊的熔点为28.1℃,相变焓为58.4 k J/kg,包覆效率为87.5%,粒径约为4.32μm,粒径分布均匀。     

微胶囊相变材料研究进展

首先介绍了微胶囊相变材料及其组成,并就微胶囊相变材料的制备方法、性能改进、性能表征以及在能量利用和热交换领域、温度控制领域和军事领域上的应用进行了综述.     

相变乳液的制备、性能与应用

相变材料是一类通过相变吸收或释放大量热量、实现热能存储和利用的材料,作为传热介质,相变材料的使用有助于热能使用效率的提高和低密度能源的开发利用。由相变材料在表面活性剂的作用下分散于传热流体中形成性能稳定的微/纳米相变乳液,是一种集储热与强化传热功能于一体的潜热型功能热流体。本文评述了相变乳液的制备及性能的研究进展,着重分析了相变乳液的稳定性、热性能及流变特性等主要性能,介绍了相变乳液的应用现状,并对相变乳液发展进行了展望。     

Novel synthesis of self-assembled CNT microcapsules by O/W Pickering emulsions

Novel carbon nanotube microcapsules were prepared by oil in water (O/W) Pickering emulsions without any surfactant used. The oxygen plasma treatment introduced several hydrophilic groups on carbon nanotubes resulting in the improved aqueous dispersion. The plasma-treated carbon nanotubes were self assembled at the interface between water and oil phases. Contact angle measurement and XPS analysis proved the hydrophilic formed on carbon nanotubes. The content of carbon nanotubes played an important role in determining both the morphology and size of microcapsules.     

Nanocellulose-stabilized Pickering emulsions and their applications

Abstract

Pickering emulsion, which is an emulsion stabilized by solid particles, offers a wide range of potential applications because it generally provides a more stable system than surfactant-stabilized emulsion. Among various solid stabilizers, nanocellulose may open up new opportunities for future Pickering emulsions owing to its unique nanosizes, amphiphilicity, and other favorable properties (e.g. chemical stability, biodegradability, biocompatibility, and renewability). In this review, the preparation and properties of nanocellulose-stabilized Pickering emulsions are summarized. We also provide future perspectives on their applications, such as drug delivery, food, and composite materials.     

Modified coconut pulp particles: The potential candidate for stabilizing Pickering emulsions

Coconut pulp, a by-product of coconut milk extraction, was used to prepare Pickering emulsion–stabilizing particles by modification with citric acid (CA) through dry heat treatment. The treatment temperature (100, 120, and 140 °C) and CA concentration (0.7, 2.0, and 3.3 % w/v) were varied. Modification at 100 °C and high concentration of CA gave products with satisfactory appearance and surface characteristics. The product obtained by treatment at 3.3 % CA and 100 °C had a yellowish white color with a light and porous surface, 0.08 degree of substitution (DS), 70° water contact angle, −50 mv zeta potential, and an average particle size after homogenization of 8.4 µm. Unmodified CP powders could not stabilize the oil-in-water (O/W) emulsion, and phase separation occurred rapidly at 25 °C, while CP modified using 2.0 % and 3.3 % CA at 100 °C could stabilize the emulsion for at least 30 d. The oil droplet size decreased as the DS of the particles increased from 77.3 to 33.3 µm and 18.6 µm for the particles with DS of 0.046, 0.072, and 0.082, respectively. The higher hydrophobicity imparted by CA modification strongly affected the oil droplet size, while the negative surface charge of particles supported the uniform dispersion of free CP particles in the interspace among the oil droplets.     

原位聚合法制备相变储热微胶囊

以三聚氰胺-甲醛为壁材,十二醇为囊芯,采用原位聚合法制备了相变储热微胶囊。采用SEM、DSC、FTIR、激光粒径分布仪等测试仪器分别测定微胶囊形态、热性能、化学成分以及粒径分布;采用光学显微镜二次聚焦法测定微胶囊的壁厚,并讨论微胶囊壁厚的影响因素。实验结果表明,当壁材／芯材用量比为1：2时,在3000r／min的乳化转速下乳化10min,80℃时固化1h制备的微胶囊粒径分布均匀,平均粒径〈10μm,且表面光洁;微胶囊壁厚随乳化转数增加而减小,而囊芯比对壁厚影响并不显著;DSC显示相变材料微胶囊化后并不影响其相变点,相变储热效果明显。     

纳米SiO_2改性相变储热微胶囊的制备及性能研究

以亲水型纳米SiO2粒子改性的三聚氰胺一甲醛树脂作为微胶囊壁材,以相变材料正十二醇为芯材,采用原.位聚合法,制备了纳米SiO2改性的相变储热微胶囊,研究了纳米SiO2粒子对微胶囊性能的影响,采用FTIR、DSC和SEM等方法进行了表征.结果表明,当壁材中加入适量的纳米SiO2时,纳米粒子在壁材里面分布均匀,微胶囊的相变焓提高,破损率降低,且纳米SiO2不会破坏预聚体的缩聚反应.当壁材中纳米SiO2质量分数为1%时,制备的微胶囊相变焓达148.7J/g,微胶囊破损率为23.1%.     

Interparticle photo-cross-linkable Pickering emulsions for rapid manufacturing of complex-structured porous ceramic materials

A new series of Pickering emulsions that can be photo-cured by interparticle photo-cross-linking reactions using small amounts of multifunctional acrylate (MA) monomers is proposed to rapidly manufacture complex-structured porous ceramic materials. In our new process, water in oil (w/o) Pickering emulsion was designed by vigorous mixing of water and polyethyleneimine partially complexed with oleic acid (PEI–OA)-stabilized SiO₂/toluene suspension containing small amounts of MA and a photo-radical initiator. Ultraviolet light irradiation to this w/o Pickering emulsion induced the formation of interparticle photo-crosslinks, which resulted in successful photocuring by photo-radical polymerization of MA and the Michael addition reaction between the polymerized MA and PEI–OA on the particles in the oil phase. We further applied the newly designed photo-curable Pickering emulsion and demonstrated that SiO₂ components with pores related to the dispersed aqueous phase and complexed outer structures could be shaped via silicone molding or a hybridized approach of photocuring and green machining. Because of the reduced amounts of MA used, the porous SiO₂ green components could be heat-treated using rapid heating profiles without any structural collapse for dewaxing and partial sintering.     

二氧化硅凝胶包覆十二醇微囊的制备

制备了二氧化硅凝胶包覆十二醇的微囊.囊壁材料是正硅酸乙酯水解、聚合生成的二氧化硅凝胶;囊芯材料是作为相变储能材料的十二醇,其相变点为24℃.微囊的储能密度为116.5J/g,包覆量为53.74%(wt),平均颗粒大小为8.26μm,适用于相变调温纤维.并对十二醇微囊的形成机理进行了初步探讨.     

原位聚合法制备石蜡微胶囊的工艺研究

考察了助剂类型和后处理工艺对微胶囊制备的影响。结果表明，表面活性剂的加入会影响微胶囊形成，加入4．0％的表面活性剂得不到微胶囊，而在不加助剂或加入聚乙烯醇时能够得到较高微胶囊化率的微胶囊。制备石蜡微胶囊必须考虑后处理工艺的影响，需依次用热水、乙醇和热石油醚洗涤才能除去未包覆石蜡。通过对微胶囊合成过程的分析表明，要形成石蜡微胶囊，必须使生成的物质具有在石蜡液滴表面富集的能力。尿素和甲醛反应生成的缩聚产物具有一定的表面活性，逐渐移动到两相界面，在水相中进一步反应、沉积，包覆石蜡形成微胶囊。     

新型聚合物多孔材料的制备研究进展

介绍了超浓乳液的形成及其特点,综述了超浓乳液作模板制备聚合物多孔材料的方法、机理和化学改性等方面的研究进展,并对其发展前景进行了展望.