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。     

Physicochemical properties and mechanical characters of methanol-modified melamine-formaldehyde (MMF) shell microPCMs containing paraffin

Microcapsules containing phase change materials (microPCMs) with melamine-formaldehyde (MF) shells have been applied in many thermo-regulation or thermo-saving fields. However, it is still essential to decrease the residual formaldehyde and enhance the mechanical properties of MF shells. The objective of this work was to fabricate a series of microPCMs containing paraffin by an in situ polymerization method using methanol-modified melamine-formaldehyde (MMF) prepolymer as shell material and investigate the physicochemical properties and mechanical characters of these microPCMs. FT-IR analysis indicates that the methanol-modified method can reduce the free formaldehyde in shell material through increasing the cross-linking structure. Optical microphotographs and SEM morphologies show that the microPCMs have regular globe shape with smooth surface. With the increasing of emulsion stirring rates from 1,000 to 5,000 rpm, the average diameters decreased sharply from 27 to 2.5 μm. The phase change temperature (T _m) of microPCMs samples with the core/shell ratios of 3/1, 2/1, 1/1, and 2/1 are 22.6, 23.0, 23.4, and 23.9 °C, which are nearly equaled to the T _m of pure paraffin (22.5 °C). Mechanical properties test data show that the MMF shells have larger yield point value than that of MF shell for microPCMs with the same core/shell ratio, which means that the methanol-modified method shell can greatly enhanced the resistance of deformation for MF shells. Moreover, MMF shells can resist the interface extrusion force in epoxy resin owing to their higher yield point of enhanced MMF shell.     

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.     

Thermal stability of microencapsulated epoxy resins with poly(urea-formaldehyde)

A series of microcapsules filled with epoxy resins with poly(urea-formaldehyde) (PUF) shell were synthesized by in situ polymerization, and they were heat-treated for 2 h at 100 °C, 120 °C, 140 °C, 160 °C, 180 °C and 200 °C. The effects of surface morphology, wall shell thickness and diameter on the thermal stability of microcapsules were investigated. The chemical structure and surface morphology of microcapsules were investigated using Fourier-transform infrared spectroscope (FTIR) and scanning electron microscope (SEM), respectively. The thermal properties of microcapsules were investigated by thermogravimetric analysis (TGA and DTA) and by differential scanning calorimetry (DSC). The thermal damage mechanisms of microcapsules at lower temperature (<251 °C) are the diffusion of the core material out of the wall shell or the breakage of the wall shell owing to the mismatch of the thermal expansion of core and shell materials of microcapsules. The thermal damage mechanisms of microcapsules at higher temperature (>251 °C) are the decomposition of shell material and core materials. Increasing the wall shell thickness and surface compactness can enhance significantly the weight loss temperatures (T_d) of microcapsules. The microcapsules with mean wall shell thickness of 30 ± 5 μm and smoother surface exhibit higher thermal stability and can maintain quite intact up to approximately 180 °C.     

Effects of ammonium chloride and heat treatment on residual formaldehyde contents of melamine-formaldehyde microcapsules

Microencapsulated n-octadecane with melamine–formaldehyde resin (MF) shell was synthesized by in situ polymerization. Ammonium chloride was used to reduce the residual formaldehyde content of microencapsulated phase change materials (microPCMs) caused by the inherent characteristics of MF. Moreover, microPCMs were heat-treated at 160 °C for 30 min. The surface morphology of the microPCMs fabricated at various microencapsulation periods was examined, and the shell thickness was measured. The effects of heat treatment on the surface morphology, residual formaldehyde content, phase change properties, and thermal stability of the microcapsules were systematically investigated. The globular surface of microcapsules fabricated at microencapsulation period of 120 min was smooth and compact with an average diameter about 2.2 μm, and the shell thickness was ranged from 30 to 70 nm. The thermal stability of heat-treated microcapsules enhanced significantly as microencapsulation period increased; in addition, the residual formaldehyde content of microcapsules decreased from 125 ± 1 mg/kg to 19 ± 1 mg/kg.     

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。     

Microfluidic fabrication of polysiloxane/dimethyl methylphosphonate flame‐retardant microcapsule and its application in silicone foams

A novel and versatile route for fabricating flame‐retardant microcapsules via microfluidics technology is reported. The flame‐retardant microcapsules were prepared with a dimethyl methylphosphonate (DMMP) core and an ultraviolet‐curable (UV‐curable) polysiloxane shell. Furthermore, a UV‐curable polysiloxane was synthesized. The synthesis mechanism of UV‐curable polysiloxane and the curing mechanism of flame‐retardant microcapsules were analyzed. To verify that DMMP was encapsulated in the microcapsules, X‐ray fluorescence was used before and after microencapsulation. The resulting microcapsules were well monodispersed and exhibited a good spherical shape with a smooth surface. In addition, the size of the microcapsules decreased dramatically with an increasing flow‐rate ratio of the middle‐/inner‐phase or outer‐phase flow rate. The thermal stability of the microcapsules was worse than shell materials but superior to DMMP. Silicone foams (SiFs) with microcapsules prepared using a dehydrogenation method achieved a relatively higher limiting oxygen‐index value than the pure SiF, which indicated that the microcapsules could enhance the flame retardation of SiFs effectively. Because of the polysiloxane shell, the microcapsules had good compatibility with SiFs, and the influence of microcapsules on the mechanical properties of SiFs was unremarkable.     

New Polyurethane/Docosane Microcapsules as Phase‐Change Materials for Thermal Energy Storage

Polyurethane microcapsules were prepared by mini‐emulsion interfacial polymerization for encapsulation of phase‐change material (n‐docosane) for energy storage. Three steps were followed with the aim to optimize synthesis conditions of the microcapsules. First, polyurethane microcapsules based on silicone oil core as an inert template with different silicone oil/poly(ethylene glycol)/4,4′‐diphenylmethane diisocyanate wt % ratio were synthesized. The surface morphology of the capsules was analyzed by scanning electronic microscopy (SEM) and the chemical nature of the shell was monitored by Fourier transform infrared spectroscopy (FT‐IR). Capsules with the silicone oil/poly(ethylene glycol)/4,4′‐diphenylmethane diisocyanate 10/20/20 wt % ratio showed the best morphological features and shell stability with average particle size about 4 μm, and were selected for the microencapsulation of the n‐docosane. In the second stage, half of the composition of silicone oil was replaced with n‐docosane and, finally, the whole silicone oil content was replaced with docosane following the same synthetic procedure used for silicone oil containing capsules. Thermal and cycling stability of the capsules were investigated by thermal gravimetric analysis (TGA) and the phase‐change behavior was evaluated by differential scanning calorimetry (DSC).     

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.     

Dielectric measurement of a single sub-millimeter size microcapsule

A new technique is described for measuring dielectric dispersion of a single microcapsule in suspension over a frequency range from 1 kHz to 10 MHz. It was applied to polystyrene microcapsules which showed a two-step dielectric dispersion, that is, a superposition of two Debye type dispersions. The dielectric dispersion was analyzed by an electrical model in which a spherical core covered with a shell is immersed in a continuous phase, yielding the phase parameters related to the microcapsule: the wall thickness, the permittivity and conductivity of the core phase. The advantage of this technique is that it can characterize individual microcapsules, whereas the conventional method provides average properties of many microcapsules. Hence, the technique enables us to directly determine the distributions of the phase parameters and to exactly examine the relationship between the dielectric behavior and the microcapsule structure simultaneously observed by microscopy.     

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.     

Microencapsulation of octadecane as a phase-change material by interfacial polymerization in an emulsion system

 Microcapsules containing phase-change material for thermal adaptable fiber application were synthesized and characterized. The microcapsules of about 1 μm in diameter were prepared using an interfacial polycondensation method with toluene-2,4-diisocyanate (TDI) and diethylenetriamine (DETA) as monomers in an emulsion system. Octadecane was used as a phase-change material and NP-10 which is nonionic surfactant, was used as an emulsifier. To investigate the reaction ratio of monomers, microcapsules were synthesized with 3 g TDI and 0–4 g DETA. Polyurea microcapsules were formed not only by reaction with TDI and DETA, but also by reaction of TDI with hydrolyzed TDI at the interface. TDI was reacted with DETA in the weight ratio of 3:1. NP-10 was reacted with TDI to form urethane. The microcapsules containing octadecane showed a phase change of octadecane at 29–30 °C. The core content measured using the heat of fusion of octadecane was less than that calculated. The efficiency of octadecane encapsulation increased as the core content decreased. Received: 17 July 2001 Accepted: 13 September 2001     

Multicomponent latex IPN materials. I. Morphology control

A series of novel structured latex particles with interpenetrating polymer network (IPN) cores and glassy SAN shells were developed in an attempt to investigate the feasibility of these polymers as both toughening and damping agents in thermoplastics. The IPN cores were composed of one impact part (polybutadiene based) and one damping part (acrylic based, with T_g around +10°C). The particle morphologies of these polymers were determined by TEM. The glass transitions and mechanical behavior of the polymers were characterized from DMS. The effect of different components on the final core/shell particle morphologies and mechanical properties was studied. The mechanical behavior of core/shell particles with IPN cores was also compared with that of separate core/shell and multilayered core/shell particles. In addition, normal core/shell synthesis (rubbery part first then the glassy part) and inverted core/shell synthesis (glassy part first then the rubbery part) were performed to provide another access for morphology control. It was found that the core/shell latex particles with poly(butyl acrylate) based copolymers are more miscible than poly(ethylhexyl methacrylate)-based copolymers. The high grafting efficiency of poly(butyl acrylate) plays an important role in governing phase miscibility. The latex particles synthesized by the inverted core/shell mode showed higher miscibility than the normal synthesized ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2193–2206, 1997     

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.     

Novel polyphenylene oxide microcapsules filled with epoxy resins

Novel polyphenylene oxide (PPO) microcapsules filled with epoxy resins (PPOMCs) were synthesized by in situ polymerization technology with 2, 6‐dimethy phenol as shell materials and diglycidyl ether of bisphenol A epoxy resins as core materials. The structures and morphologies of PPOMCs were characterized using Fourier‐transform infrared spectroscopy, micro‐confocal Raman microscope, laser scanning confocal microscopy, scanning electron microscopy and optical microscopy, respectively. The thermal properties of PPOMCs were investigated using differential scanning calorimetry and thermogravimetric analysis. The influences of different processing parameters such as the weight ratio of shell material to core material, kind of surfactant and reaction temperature on the morphologies and sizes of PPOMCs were investigated. Preliminary investigation on application of PPOMCs to thermosetting resins 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) system was conducted. Results indicate that PPOMCs can be synthesized successfully. The sizes and surface morphologies of PPOMCs may be significantly affected by different processing parameters. PPOMCs can be well prepared at about 30°C, and they depend strongly on the kind of surfactant and the weight ratio of shell material to core material. PPOMCs basically exhibit high thermal stability when the temperature is below 258°C. The addition of PPOMCs can improve the mechanical properties and maintain the thermal properties of BMI/BA system. The released core materials from PPOMCs may repair the matrix cracks through the polymerization of epoxy resins initiated by curing agent. Copyright © 2012 John Wiley & Sons, Ltd.     

Microencapsulation of a functional dye and its UV crosslinking controlled releasing behavior

A new family of microcapsules containing photopolymerizable tripropylene glycol diacrylate (TPGDA) was synthesized by using interfacial polymerization. The release behavior of encapsulated dye could be controlled easily by changing the crosslink density of network formed from TPGDA. The chemical structure and properties of microcapsules were characterized by Fourier Transform infrared spectroscopy, scanning electron microscope, differential scanning calorimetry, optical microscope, wide angle X‐ray diffraction and UV‐visible spectrophotometer. The results demonstrate that the higher agitation rate results in a smaller particle size with a narrow size distribution. When core/shell ratio is low, the surface of the microcapsules becomes smooth. Additionally, it was found that UV radiation time is most effective factor to change the C?C double bond conversion ratio. After microcapsules were synthesized, the release speed could be changed according to requirement by exposing them to UV light for minutes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3630–3639, 2009     

Urea-Formaldehyde Microcapsules Containing an Epoxy Resin: Influence of Reaction Parameters on the Encapsulation Yield

In this work urea-formaldehyde microcapsules containing an epoxy resin are prepared by in situ polymerization of monomers in an oil-in-water emulsion. Scanning electronic microscopy (SEM) was performed to investigate on microcapsule size and surface morphology. Calorimetric and spectroscopic analyses were carried out with the aim of evaluate the encapsulation yield and the shell features. Factors determining the microencapsulability of the core material were described. In particular, our interest was devoted to a better understanding of the influence of the reaction parameters on the microcapsule properties. It was found that the encapsulation yield as well as the extent of urea-formaldehyde polymerization depends on the reaction temperature and the stirring speed.     

Structure and thermal stability of microencapsulated phase-change materials

A series of microcapsules containing n-octadecane with a urea-melamine-formaldehyde copolymer shell were synthesized by in-situ polymerization. The surface morphology, diameter, melting and crystallization properties, and thermal stability of the microcapsules were investigated by using FTIR, SEM, DSC, TGA and DTA. The diameters of the microcapsules are in the range of 0.2–5.6 m. The n-octadecane contents in the microcapsules are in the range of 65–78wt%. The mole ratio of urea-melamine has been found to have no effect on the melting temperature of the microcapsules. Two crystallization peaks on the DSC cooling curve have been observed. The thermal damage mechanisms are the liquefied n-octadecane leaking from the microcapsule and breakage of the shell due to the mismatch of thermal expansion of the core and shell materials at high temperatures. The thermal stability of materials can be enhanced up to 10 °C by the copolymerization of urea, melamine and formaldehyde in a mole ratio 0.2:0.8:3. The thermal stability of 160 °C heat-treated microcapsules containing 8.8% cyclohexane can be further enhanced up to approximately 37 °C.     

The role of microstructure on the mechanical properties of polyurethane foams containing thermoregulating microcapsules

Rigid polyurethane foams with up to 50 wt% of microcapsules from LDPE-EVA containing Rubitherm^®RT27 were synthesized. The influence of microcapsules on the foams density, microstructure and mechanical resistance was studied. Cell size and strut and wall thicknesses were analyzed by SEM. The relationships between densities and foam microstructures with their Young's moduli and collapse stress were found by the Gibson and Ashby formulations and the Kerner equation for mechanical properties of composites. It was found a cell structure change from polyhedral closed-cells to spherical or amorphous open-cells. A good agreement between the experimental and theoretical data was observed but requiring a cell form factor. Thus, Fitting parameters confirmed the high trend of these microcapsules to be incorporated into the foam cell walls and the form factors depicted the abrupt change of cell morphology. Thus, these equations are suitable for predicting the mechanical properties of foams containing fillers of low mechanical resistance.     

Preparation of PCM microcapsules by complex coacervation of silk fibroin and chitosan

Phase change material microcapsules were prepared by complex coacervation of silk fibroin (SF) and chitosan (CHI). n-Eicosane was used as the core material. The effects of SF/CHI ratio, and percentage of cross-linking agent and n-Eicosane content on the properties of microcapsules were studied. The size distribution and the surface morphology of microcapsules were characterized by optical and scanning electron microscopy. The encapsulation of core material was determined by energy dispersive spectrometer analysis. The results indicated that SF/CHI microcapsules were prepared successfully. Microcapsules had smooth outer surface when the ratio of SF to CHI was close to 5. On the other hand, at high SF/CHI ratios (≥14), microcapsules showed a two-layer structure, an inner compact layer, and an outer, more porous, sponge-like layer. The highest microencapsulation efficiency was obtained at a SF/CHI ratio of 20 in the presence of 0.9% cross-linking agent and of 1.5% n-Eicosane content.