Dielectric study of poly(methyl methacrylate) microcapsules in particular reference to the effect of the frequency dependence of the permittivity of the capsule wall

The dielectric behavior of poly(methyl methacrylate) (PMMA) microcapsules was analyzed theoretically by taking account of the frequency dependence of the relative permittivity _s and the electrical conductivity _s of the capsule wall. For comparison, similar analysis was applied to polystyrene (PS) microcapsules which have frequency-independent _s and _s . The behavior of _s and _s of the PMMA microcapsules was assumed to be represented by a dielectric relaxation of them-th power type on the basis of dielectric data on underwater PMMA films. By means of a theory of the interfacial polarization, some consideration was carried out regarding the effect of the frequency dependence of _s and _s on the dielectric behavior of the PMMA microcapsules. The consideration led to predictions that the frequency dependence of _s and _s causes (i) the variation in the relaxation intensity with the change in the conductivity of suspending medium, (ii) the frequency dependence of the permittivity at low frequencies and (iii) the frequency dependence of the conductivity at high frequencies. The theoretical prediction (i) was verified by observed data, (ii) and (iii) remaining unverified owing to the experimental difficulty.     

Preparation and properties of thermosensitive hydrogel microcapsules

Temperature-sensitive hydrophilic gel microcapsules have been newly prepared. That is, poly ( -lysineisopropylamide–terephthalic acid) microcapsules containing water have been obtained by an interfacial polymerization at a water/oil interface between -lysineisopropylamide and terephthaloyldichloride. The microcapsule changes its size between 33 and 35°C. Under 33°C, the microcapsules are fully spherical and can be redispersed in distilled water, while are aggregated above 35°C. The microcapsules, which are observed to show aggregation above 33°C, can be redispersed by decreasing temperature within a few second. The thermosensitive morphological changes of the microcapsules are thus reversible. Also, it has been shown that the permeability of sodium chloride through the microcapsule membrane changes remarkably between 33 and 35°C, while it is kept almost constant independent of temperature between 25 and 33°C or between 35 and 55°C. The permeability of solutes is higher under 33°C than that above 35°C. Such thermosensitive properties result from the fact that the polymer membrane has isopropylamide groups. That is, -lysineisopropylamide has a chemical structure similar to N-isopropylacrylamide, the polymer of which, poly (N-isopropylacrylamide), is a thermosensitive hydrogel having its phase transition temperature around 33°C.     

海藻酸钠-壳聚糖-桑椹红微囊的制备

以海藻酸钠-壳聚糖为复合囊材采用锐孔法制备桑椹红微囊,探讨了海藻酸钠浓度、壳聚糖浓度、Ca Cl2浓度、桑椹红浓度、针头孔径、下滴高度、温度、转速等因素对微囊包封率的影响。确定了最佳制备工艺条件为海藻酸钠浓度4.0%、壳聚糖浓度2.5%、氯化钙浓度2.0%、桑椹红浓度0.50%、针头孔径0.390mm、下滴高度4cm、温度为20℃、转速为300r·min-1。制得的微囊药物含量为11.28%,包封率为88.93%。     

Clay‐reinforced polyamide: Preferential orientation of the montmorillonite sheets and the polyamide crystalline lamellae

Intercalated and exfoliated nanocomposites were prepared by the extrusion and injection of polyamide‐6 and highly swollen or slightly swollen montmorillonite, respectively. The microstructure of pure compounds was characterized. The basal spacing was more homogeneous in swollen montmorillonite than in nontreated montmorillonite. This was attributed to the presence of a surfactant. Surfactant crystallites were observed in swollen montmorillonite and in the nanocomposites. Their distribution is discussed. The nanocomposites exhibited anisotropic properties attributed to the orientation of the montmorillonite sheets. The preferential orientation of the montmorillonite sheets was studied in detail by small‐angle X‐ray scattering (SAXS). It was found to be related to the injection direction. An average distance between two sheets was also measured from the SAXS spectra. The crystallographic state of the polyamide matrix was then analyzed. The orientation of the polymer lamellae relative to the montmorillonite sheets is discussed. The orientation of the montmorillonite sheets and the polyamide lamellae is expected to play a major role in the mechanical properties of nanocomposites. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1360–1370, 2001     

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.     

Oxygen barrier properties of organic montmorillonite modified polyamide 11/Poly (vinyl alcohol) films

Organic montmorillonite (OMMT) nano‐platelets were exfoliated and well dispersed in fully bio‐based polyamide 11/Poly(vinyl alcohol) (PA11/PVA) blends. Significantly lower oxygen permeation rates (OTR) were detected for the PA11_72.5PVA_27.5OMMT_x films than those of PA11 and PA11_72.5PVA_27.5 films. An extremely low OTR of 0.218 cm³/m²·day·atm was found for PA11_72.5PVA_27.5OMMT₁ film modified with 1 PHR optimum concentration of well dispersed OMMT nano‐platelets. Similarly, the free volume characteristics evaluated for PA11_72.5PVA_27.5OMMT_x film series reduced to a minimum as the OMMT concentration reached the optimum value. As revealed by dynamic mechanical and differential scanning calorimetric analyses of PA11_72.5PVA_27.5OMMT_x film series, all dynamic glass transition temperature (T_g), melting temperature (T_m) and percentage crystallinity (W_c) values of PA11_72.5PVA_27.5OMMT_x films were noticeably higher than those of PA11_72.5PVA_27.5 film without addition of OMMT. In fact, T_gs, T_ms and W_cs evaluated for PA11_72.5PVA_27.5OMMT_x films increased to a maximum, as their OMMT reached the optimum concentration. The considerably enhanced oxygen barrier resistance found for PA11_72.5PVA_27.5OMMT_x films was ascribed to the considerably reduced free volume characteristics and much longer permeation path caused by impermeably OMMT nano‐platelets well dispersed in PA11_72.5PVA_27.5OMMT_x films.     

Preparation of poly(methyl methacrylate) microcapsules by in situ polymerization on the surface of calcium carbonate particles

Poly(methyl methacrylate) (PMMA) microcapsules were prepared by the in situ polymerization of methyl methacrylate (MMA) and N,N′-methylenebisacrylamide on the surface of calcium carbonate (CaCO₃) particles, followed by the dissolution of the CaCO₃ core in ethylenediaminetetraacetic acid solution. The microcapsules were characterized using fluorescence microscopy, atomic force microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. The average sizes of the CaCO₃ particles and PMMA capsules were 3.8 ± 0.6 and 4.0 ± 0.6 μm, respectively. A copolymer consisting of MMA and rhodamine B-bearing MMA was also used to prepare microcapsules for fluorescent microscopy observations. Fluorescein isothiocyanate-labeled bovine serum albumin was enclosed in the PMMA microcapsules and its release properties were studied.     

利用静电界面制备高性能蒙脱石/氢化丁腈橡胶

将甲基丙烯酸(MA)和烷基胺改性蒙脱石(MMT)混合成浆料后,加入到氢化丁腈(HNBR)橡胶中,通过热硫化工艺,制备了MMT/HNBR橡胶复合材料.采用扫描电子显微镜、透射电子显微镜、小角X射线衍射仪、傅里叶变换红外光谱仪和转矩流变仪研究了MA改性的MMT与橡胶间的界面及分散性,并对复合材料的各种性能进行分析.结果表明,在热硫化过程中,不仅形成了橡胶的交联网络,而且也促使MA在橡胶中发生原位聚合.生成的聚甲基丙烯酸与MMT表面的烷基胺形成离子对,从而在橡胶和MMT间构筑了强的静电界面.同时MA在MMT层间发生聚合反应,提高了MMT在橡胶中的分散性.动态机械性能和200%应变的应力松弛实验表明,良好分散的MMT和静电界面有效约束了橡胶分子链在力学拉伸过程中的运动.与纯橡胶相比,MMT/HNBR橡胶复合材料具有更大的拉伸强度和韧性.此外,橡胶复合材料还具有良好的N2气阻隔性能.因此,配制MA/MMT浆料是一种简单方便的MMT改性方法,制备的MMT/HNBR橡胶复合材料可用于制造具有高强韧性和气体阻隔性要求的橡胶产品.     

Preparation and properties of isobutylene–isoprene rubber–clay nanocomposites

Isobutylene isoprene rubber (IIR)‐clay nanocomposites have been prepared successfully by melt intercalation with maleic anhydride‐grafted IIR (Ma‐g‐IIR) and organophilic clay. In IIR‐clay nanocomposites, the silicate layers of the clay were exfoliated and dispersed into the monolayer. The nanocomposites exhibited greater gas barrier properties compared with those of Ma‐g‐IIR. When 15 phr clay was added, gas barrier properties were 2.5 times greater than those of Ma‐g‐IIR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1182–1188, 2006     

Preparation and properties of PU/MCMMT nanocomposites

The cetyltrimethyl ammonium bromide (CTAB) was used as a swelling agent to be intercalated into the galleries of the montmorillonite (MMT) platelets to get the organic MMT (CMMT). Then 4,4′‐diphenylmethane diisocyanate (MDI) were grafted on CMMT by the reaction between hydroxyls in organic MMT platelets and MDI to synthesize the MDI modified CMMT (MCMMT). Polyurethane (PU)/MCMMT composites were prepared by situ polymerization. The MCMMT platelets dispersed in a PU matrix in nanometer scale. The dispersion and intercalation degree of the MCMMT platelets decreased with increase in the content of MCMMT. Under the same content of fillers, the tensile strength and tear strength of PU/MCMMT nanocomposites were higher than those of PU/organic MMT nanocomposites. The reinforcing effect of the MCMMT platelets to the PU was better than that of the organic MMT platelets. With increase in the content of MCMMT, the tensile strength and tear strength of the PU/MCMMT nanocomposites were increased, while the extent of the increase slowed down. Compared with those of PU, the thermal stability of PU/MCMMT nanocomposites was increased. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and properties of chitosan chondroitin sulfate complex microcapsules

The chitosan (CHS) chondroitin sulfate (CS) complex microcapsules were prepared by emulsion-chemical crosslink method, with the chitosan and chondroitin sulfate as the wall materials and the low molecular weight heparin (LMWH) as the core materials. The microcapsules were characterized by Fourier transform infrared (IR) spectrometry, scanning electron microscope (SEM), size distribution and thermal analysis. The in vitro drug release behavior of the microcapsules was studied by spectrophotometry. The SEM and size distribution showed that the microcapsules were in the spherical form mostly in the size range of 20-80 microm. The IR spectrum indicated that there were electrostatic interactions between chitosan and chondroitin sulfate, with the sulfate group and free carboxyl group reacted with the amino groups of chitosan. The DSC result showed that the wall materials could protect the core materials of the microcapsules. The results of the release kinetics experiments of the microcapsules showed that the drug released slightly faster in acid media than in alkali ones.     

Controlled release properties of Chitosan encapsulated volatile Citronella Oil microcapsules by thermal treatments

This research uses modified orifice method to prepare the O/W type Chitosan encapsulated volatile Citronella Oil microcapsules. In this article, we investigated the forming condition of microcapsules and the influence to sustained release effect of volatile Citronella Oil by applying thermal pretreatment to microcapsules. The results suggest that the forming of microcapsules should be processed under the fundamental conditions of: (1) the concentration of Chitosan is at least 0.2 wt%, (2) NaOH is greater than 0.1 wt%, and (3) with the additive of coconut oil as natural surfactant, so that we could obtain final product of microcapsules with better formation and dispersion. The changes in concentration of Chitosan will affect the encapsulation efficiency of the volatile Citronella Oil. When the concentrations of Chitosan are 0.5%, 1.0% and 1.5%, the encapsulation efficiencies are 98.2%, 95.8% and 94.7%, respectively. The particle size of Chitosan microcapsules would decrease as the emulsification stirring speed increases. When the stirring speeds are 400 rpm, 800 rpm, and 1500 rpm, the average particle sizes of microcapsules produced are 225 ± 24 μm, 131 ± 20 μm, and 11 ± 3 μm, respectively. If the microcapsules were thermal pretreated at 80 °C, the structure of Chitosan wall membrane would shrink and thus achieve the effect of sustained release. The sustaining effect would increase along with treatment time increases.     

Preparation and mechanical properties of thermal energy storage microcapsules

A series of heat energy storage microcapsules was prepared using melamine-formaldehyde resin as the shell material and the mechanical properties of the shell were investigated. A phase change material whose melting point was 24 °C was used as core and the quantity of heat involved in phase transition was 225.5 J/g. Average diameter of the microcapsules varied from 5 to 10 μm, and the globular surface was smooth and compact. The mechanical properties of the shell were evaluated by observing the surface morphological structure change after application of pressure by means of scanning electron microscopy. When the mass ratio of the core and shell material is 3:1, a yield point of about 1.1×10⁵ Pa was found and when the compression was increased beyond this point the microcapsules showed plastic behavior. This has been attributed to the cross-link density and to the high degree of reaction of the shell material. Different yield points subsequently reflected differences in the mechanical behavior. It was also found that the mechanical intensity of double-shell microcapsules was better than that of single shelled ones.     

Contribution of nanoclays to the barrier properties of a model proton exchange membrane for fuel cell application

Direct methanol fuel cells (DMFCs) that use a proton exchange membrane (PEM) as electrolyte, is a promising alternative source of energy for the future. However, methanol crossover from the anodic side to the cathodic one is a major problem in DMFC. Proper dispersion of layered silicates within the fuel cell membrane has been proposed as a strategy for improving the barrier properties of the membrane. The validity of this approach has been tested in case of a model membrane consisting of phosphotungstic acid doped poly(vinyl alcohol). A solvent casting technique has been used, which allows the nanofiller to be delaminated by an ultrasonic pre-treatment, as confirmed by TEM and XRD analysis. The layered silicates have a favourable impact on the methanol permeability, whose the decrease overcompensates some loss in ionic conductivity.     

仿生微胶囊的组装及其应用

在生物物理和生物医药研究领域中,在分子水平上组装功能化的仿生微胶囊具有重要的理论和应用价值.在现有制备微胶囊的技术手段中,层层组装技术以其能够控制胶囊的尺寸、形状、囊壁的厚度和组成以及易于实现功能化等特点,引起了人们越来越多的研究兴趣.本文将着重介绍如何利用层层组装技术,以磷脂、蛋白质和其他生物大分子为组装基元构筑仿生微胶囊、以及如何将微胶囊进行生物界面化的修饰.此外,以仿生微胶囊为药物载体,探讨其在光动力治疗方面的应用也作简单介绍.     

CoCl_2-PVA可逆热敏微胶囊的制备与性能

以低温可逆热敏示温材料氯化钴（CoCl2）为芯材、聚乙烯醇（PVA）为壳材、戊二醛（GA）为交联剂,在W/O/W混合乳液体系中,通过界面交联法制备了CoCl2-PVA可逆热敏示温微胶囊,并对其各项性能进行了系统研究。结果表明：当PVA溶液的质量分数为0.8%、PVA与GA摩尔比为1∶2.5、内水相pH为2、CoCl2溶...     

微胶囊化石蜡的制备和热性能

微胶囊化石蜡的制备和热性能;微胶囊;原位聚合法;相变材料;差示扫描量热法     

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.     

铀酰萃取剂双亚砜的合成及其微胶囊萃取铀性能的研究

铀是一种非常重要的能源物质 ,现在国际上一般使用磷酸三丁酯 (ＴＢＰ)作为铀的萃取剂提取及回收铀。ＴＢＰ对铀有较强的萃取能力 ,但它耐辐照能力较差 ,有关双亚砜的报道仅局限于ｎ =1 ,2 [1,2 ] 。本文以硝酸为氧化剂 ,采用硫醚氧化法 ,合成了四个新的双亚砜类化合物ＰｈＳＯ(ＣＨ2 ) ｎＳＯＰｈ(ｎ分别为 2、3、4、6) ,并经元素分析、核磁共振对其结构进行了表征。为避免萃取过程中乳化或三相的出现 ,采用界面缩聚法[3 ] 以高分子材料包覆ＴＢＰ和自制的双亚砜类化合物 (ｎ =2 ,4,6) ,制成微胶囊 ,对其在酸性水溶液 (ｐＨ =1～1 .5 )中萃…