聚苯乙烯/聚甲基丙烯酸甲酯核/壳结构复合乳液的制备与形貌的研究

采用多步种子乳液聚合的方法 ,经过制种、合成核和合成壳 3个步骤 ,制备了具有核 /壳结构的聚苯乙烯(PS) /聚甲基丙烯酸甲酯 (PMMA)复合乳液 ,考察了制备条件对形成的复合乳液粒子的大小的影响。用透射电镜考察了复合乳液的形貌 ,发现乳液粒子的粒径在纳米级 ,预计在某些领域会有特殊用途。     

两亲性温度及pH敏感性嵌段共聚物PMMA-b-(PAA-co-PNIPAM)的合成与表征

采用可逆加成断裂链转移自由基聚合方法,成功地制备了两亲嵌段共聚物聚甲基丙烯酸甲酯-b-聚丙烯酸-co-聚异丙基丙烯酰胺(PMMA-b-(PAA-co-PNIPAM)。利用傅立叶红外光谱、核磁共振和透射电镜研究了共聚物的结构特征;用GPC测定了其分子量和分子量分布。透射电镜、激光粒度分析仪和动态光散射结果表明嵌段共聚物在水溶液中能够自组装形成直径为200nm的胶束颗粒。通过紫外-可见分光光度计和差示扫描量热法测得了不同pH值下嵌段共聚物的低临界溶解温度(LCST)。经过接枝后的嵌段共聚物的LCST比PNIPAM要高,且随着pH值的降低,聚合物的LCST随之降低。聚合物的LCST可以通过AA链段与NIPAM链段的比例、温度、pH值来控制。     

超小型Fe3O4/Au纳米复合微粒的制备与表征

用反向微乳液法成功制备了超小型Fe3O4/Au磁性纳米复合微粒,并利用3-巯基丙酸将复合微粒直接从微乳液分离到有机溶剂中.用UV-Vis、VSM和TEM对产物进行了鉴定与表征,结果表明复合微粒分散良好,平均粒径为6.7nm,饱和磁化强度为9.7A·m2/kg.     

嵌段共聚物偶联剂的合成及其胶束化行为

采用阴离子聚合反应合成了可作为纤维增强聚合物复合材料界面改性偶联剂的苯乙烯/丁二烯/乙烯基三乙氧基硅烷及苯乙烯/异戊二烯/乙烯基三乙氧基硅烷嵌段共聚物,通过傅立叶红外光谱(FT-IR)、核磁共振氢谱(1H-NM R)等分析手段对合成产物进行了表征,并采用透射电镜(TEM)、动态激光光散射(DLLS)等技术研究了嵌段共聚物在溶剂中的组装行为。结果表明,反应合成了预定结构的嵌段共聚物偶联剂,该共聚物在选择性溶剂中能形成以可溶性链段为壳、难溶性链段为核的胶束结构,胶束的粒径与共聚物分子链及各嵌段的长度有关。     

Preparation of controllable core-shell gold nanoparticles and its application in detection of silver ions

We report a novel shell technique to prepare controllable core-shell nanoparticles. In this technique, the shell is formed when the core reacts with metal ions and Na(2)S(2)O(3) and the size of the core and thickness of the shell can be controlled. Transmission electron microscopy and X-ray diffraction reveal that the shell consists of insoluble complex salts comprising Au(2)S, AuAgS, and Ag(3)AuS(2). The resulting core-shell nanoparticles obtained at different reaction stages demonstrate that the formation of Au(2)S, AuAgS, and Ag(3)AuS(2) shell proceeds from the outside. The morphological evolution of the particles changes significantly with reaction time demonstrating that formation of the shell results from diffusion in the solid shell. The core-shell nanoparticles produced by this technique can be used as nanosensors to detect Ag(+) in aqueous media with high selectivity and sensitivity. The excellent selectivity for Ag(+) is demonstrated by comparing the response to other metal ions. In addition, our evaluation indicates that gold nanorods offer higher sensitivity than gold nanospheres.     

一种全亲水两嵌段共聚物的多重胶束化

以1-氯代乙苯为引发剂,氯化亚铜/N,N,N′,N″,N″-五甲基二乙撑三胺(PMDETA)为催化体系,通过连续原子转移自由基聚合(ATRP)合成了聚丙烯酸叔丁酯-b-聚(甲基丙烯酸二甲胺基乙酯)(PtBA-b-PDMAEMA),然后用三氟乙酸将其水解,得到一种全亲水的嵌段共聚物聚丙烯酸-b-聚(甲基丙烯酸二甲胺基乙酯)(PAA-b-PDMAEMA)。将其溶于水中,只需要调节水的pH值就可以调节聚合物自组装完成从正向胶束到反向胶束的转变。在pH为2.4时,嵌段共聚物自组装形成以PDMAEMA为核,PAA为壳的核壳结构胶束(Dh=253.4 nm);当pH升高到10.0时,共聚物自组装形成核壳结构相反的反向胶束(Dh=279.9 nm)。进一步用动态光散射和透射电镜对胶束的温度敏感性进行了初步研究。     

Effect of Shell Coating Techniques on Dynamic Response of Photoconductive Core/Shell Nanorod Arrays

Efficient carrier collection in the core/shell nanowire (nanorod) arrays requires a high quality interface between core and shell materials. A highly conformal shell layer around nanorods can lead to fast dynamic response in photoconductive devices by a radial charge flow. Therefore, choice of the deposition technique for the conformal shell layer becomes crucial. In this study, the dynamic response of indium sulfide (In₂S₃) nanorods/silver (Ag) core/shell devices is compared in which Ag shell layers are deposited by different physical vapor deposition (PVD) techniques. In₂S₃ nanorods are fabricated by glancing angle deposition. The core/shell devices with Ag shell sputtered at a relatively high working gas pressure (≈3 × 10⁻² mbar) produce the highest photocurrent compared to other devices in which more directional incident flux (with working gas pressure of ≈3 × 10⁻³ mbar) is utilized for Ag shell layer. The reduced transit times indicate a conformal shell achieved by the high pressure sputtering technique that has a wide angular distribution flux. In addition, a more directional flux yet with a small angle (≈30°) incidence with respect to the substrate surface normal also helps increase the photocurrent. Such simple and scalable PVD techniques are shown to offer alternative fabrication approaches in producing high quality core/shell nanostructures.     

Fabrication of polymer-silica core-shell particles using copolymeric spheres prepared via precipitation polymerization

Silica-coated polymeric particles were synthesized based on cationic colloidal particles which were prepared by precipitation polymerization of divinylbenzene in the presence of a cationic monomer, N-[3-(dimethylamino)propyl]methacrylamide. Negatively charged silica precursors were interacted with the cationic charged dimethylamine groups in colloidal particles. The resulting polymer/silica core/shell particles were characterized by scanning electron microscopy (SEM). Moreover, omniphobic particles were achieved by coupling reaction of the core/shell particles with nonafluorohexyl-triethoxysilane. Their water/oil static contact angles were investigated.     

PS／P（BA－BOA）核壳乳液的研究

以丁氧基甲基丙烯酰胺（ＢＯＡ）为活性单体，采用种子乳液聚合法制备了ＰＳ／Ｐ（ＢＡ－ＢＯＡ）核壳型复合乳液，用透射电子显微镜观察了乳液粒子的微观形态，探讨了聚合方式等对微观结构的影响，对乳液的稳定性以及乳液膜的力学性能进行了测试，考察了聚合方式对乳液性能的影响。     

A method for synthesizing the core (Ag)/shell (PSt) composite nanoparticles

Core-shell composite materials have been widely used in many fields. In this paper, the core (Ag)-shell (PSt) composite nanoparticles have been successfully fabricated in microemulsions at ambient pressure. Firstly, Ag nanoparticles with about 60-100 nm in diameters were synthesized by reducing silver nitrate by ascorbic acid, and then, styrene polymerized at the surface of Ag nanoparticles by K₂S₂O₄ initiator in microemulsion solutions. The Ag/PSt core-shell composite nanoparticles were identified by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and infrared spectra (IR). Results show that Ag-core nanoparticles were coated with ultra thin PSt shell with thickness of about 3-6 nm.     

钛酸钡/钡铁氧体核/壳粒子的电磁性能

在以尿素为沉淀剂制备钛酸钡(BaTiO₃)/钡铁氧体(BaFe₁₂O₁₉)核/壳粒子的基础上, 采用透射电子显微镜(TEM)、X射线衍射分析仪(XRD)、傅里叶变换红外光谱仪(FT-IR)对BaTiO₃/BaFe₁₂O₁₉核/壳粒子前驱物及BaTiO₃/BaFe₁₂O₁₉核/壳粒子的形貌、结构和成份进行了表征, 采用网络矢量分析仪对BaTiO₃/BaFe₁₂O₁₉核/壳粒子的电磁特性进行了研究. 结果表明, 均匀共沉淀制得的BaTiO₃/BaFe₁₂O₁₉粒子呈现核/壳结构, BaFe₁₂O₁₉壳层对BaTiO₃的包覆均匀、完整、光滑; 在2~7GHz, BaTiO₃/BaFe₁₂O₁₉核/壳粒子的ε′和ε″分别为10.7~17.0和0.3~0.6, 均高于BaTiO₃. ε′和ε″的增大是核/壳结构所引起的界面极化加强的结果; BaTiO₃/BaFe₁₂O₁₉核/壳粒子出现了BaTiO₃所没有的磁性能, 其μ′和μ″在2~7GHz远远高于BaTiO3, 表现出了较为明显的磁损耗, 这与磁性BaFe₁₂O₁₉壳层的包覆有关.     

Uniformly gold nanoparticles derived from P2VP-b-PCHMA block copolymer templates with different reduction methods

The micellization of poly(2-vinylpyridine)-block-poly(cyclohexyl methacrylate) (P2VP-b-PCHMA) in THF can be induced by the complexation between the P2VP blocks and HAuCl4, forming composite polymeric micelles with PCHMA being the shell and P2VP/HAuCl4 complex being the core. In order to obtain regular arrays of gold nanoparticles (Au NPs), monolayer of HAuCl4-loaded surface micelles have been produced by spin-coating the micellar solution, and Au NPs in different size have been obtained by oxygen plasma with different reduction processes. In addition, pyrole (PY) has been used as an efficient reducing agent to fabricate dispersed Au NPs within micellar structure in a short reducing time, resulting in a raspberry-like morphology of the Au-polymer composites. With the addition of annealing processes or longer reducing time (one month), different shapes of Au NPs have been observed in the cast films. Furthermore, core-shell nanostructures of gold-polypyrole (Au-PPY) have also been observed by employing vapor phase polymerization of PY onto HAuCl4-loaded polymeric solution-cast films.     

工艺参数对聚脲甲醛包覆环氧树脂微胶囊物性的影响

以聚脲甲醛为囊壁、双酚A 型环氧树脂( E-51) 和正丁基缩水甘油醚(501 # ) 混合物为囊芯, 采用原位聚合法合成聚脲甲醛包覆环氧树脂体系微胶囊。通过L16 (45 ) 正交试验研究了原料配比、终点p H 值、搅拌速率、酸化时间、平均升温速率等工艺参数对微胶囊的合成状态、粒径大小和分布的影响规律, 并利用扫描电子显微镜(SEM) 、光学2摄影显微镜(OM) 进行表征。结果表明: 原料配比和终点p H 值对微胶囊的合成状态有显著影响;适当延长酸化时间和增加升温速率, 有利于增加微胶囊表面的粗糙度; 随着搅拌速率的增加, 微胶囊的粒径减小、分布变窄。优化的工艺条件为: 原料配比为0. 8∶1 , 终点p H = 2. 0～4. 0 , 酸化时间为2. 0～3. 0 h , 升温速率为0. 17～0. 25 ℃·min -1 , 搅拌速率为325～350 r·min -1 。      

Optical properties of core–shell structured Ag/SiO2 nanocomposites

Silver nanoclusters coated by SiO₂ were synthesized by a reverse micelle technique to obtain a core–shell microstructure with tunable particle size less than 50 nm. The refractive indices of the Ag/SiO₂ nanocomposites were calculated based on a theoretical model for binary composite materials which illustrated a strong correlation to the size of the metallic core and the dielectric shell. Dynamic light scattering analysis of the Ag/SiO₂ nanocomposites revealed that the refractive index of the nanocomposites was about 2.40, which was well in the range predicted by theoretical modeling. Optical absorption spectra and silver quantum dot size induced color change of the Ag/SiO₂ nanocomposites suspension were also investigated.     

Facile synthesis of 1-(N-butyl-1,8-naphthalimide-4′-yl)-3-(4-methoxyl-phenyl)-5-phenyl-pyrazoline/polyaniline core-shell nanofibers and polyaniline nanotubes

1-(N-butyl-1,8-naphthalimide-4′-yl)-3-(4-methoxyl-phenyl)-5-phenyl-pyrazoline (BMPP)/polyaniline core-shell nanofibers were synthesized by in situ chemical oxidative polymerization of aniline using BMPP nanofibers as template. BMPP/polyaniline core-shell nanofibers exhibited uniform fibrilliar morphology and possessed BMPP nanofiber core and polyaniline shell, which existed in the form of nanoparticles. BMPP nanofibers were fabricated by the modified reprecipitation method with water as poor solvent. After BMPP/polyaniline core-shell nanofibers were washed with ethanol as good solvent to remove BMPP cores, polyaniline nanotubes with netlike structures were obtained. The molecular structures of BMPP/polyaniline nanocables were characterized by Fourier transform infrared spectroscopy and UV-vis spectroscopy, respectively. The core/shell structures of BMPP and polyaniline endowed BMPP/polyaniline core-shell nanofibers good electrochemical properties in comparison with BMPP nanofibers.     

Preparation of nickel–silver core–shell nanoparticles by liquid-phase reduction for use in conductive paste

Nickel–silver (Ni–Ag) core–shell nanoparticles (NPs) were prepared by depositing Ag on Ni nanocores using the liquid-phase reduction technique in aqueous solution, and their properties were characterised using various experimental techniques. The core–shell NPs had good crystallinity, and the thicknesses of the Ag nanoshells could be tuned effectively. The oxidation resistance of the Ag surface and the electroconductive properties of the Ni core allowed these Ni–Ag core–shell NPs to be used in a conductive paste. Thick films composed of Ni–Ag core–shell NPs were screen-printed on a polycrystalline silicon substrate then sintered at temperatures ranging from 500 °C to 800 °C. Stable resistivity was obtained when the sintering temperature was higher than 650 °C, and the electrical properties of the Ni–Ag core–shell paste were close to those of pure Ag paste. Thus, the Ni–Ag NPs can partly replace pure Ag NPs in conductive pastes.     

钯纳米粒子/嵌段共聚物复合胶束的制备及催化性能

嵌段共聚物聚苯乙烯-b-聚4-乙烯吡啶(PS-b-P4VP)在酸水(pH=2)中自组装形成PS为核,P4VP为壳的核-壳胶束(约为30 nm)。在核-壳胶束酸水溶液(pH=2)中加入氯化钯,钯离子与P4VP络合形成聚苯乙烯为核、聚4-乙烯吡啶/钯离子为壳的胶束。进一步加入硼氢化钠(NaBH4)原位还原钯离子,得到钯纳米粒子(粒径约为3 nm)位于P4VP壳层的复合胶束。复合胶束对4-硝基苯酚还原为4-氨基苯酚的反应中表现出催化活性,动力学研究结果表明,反应为一级反应,反应速率随复合胶束浓度的增加及反应温度的升高而加快。     

In situ controllable synthesis of Ag@AgCl core–shell nanoparticles on graphene oxide sheets

Graphene oxide-supported uniform Ag@AgCl core–shell nanoparticle composites have been successfully prepared by a facile two-step synthetic process. First, graphene oxide sheets were used as carriers to anchor and disperse Ag nanoparticles on their surface. Then these fixed Ag nanoparticles on carbon sheets are utilized as precursors, around which AgCl nanocrystals form in situ using FeCl₃ as oxidant, forming graphene oxide-supported Ag@AgCl core–shell nanoparticle composites. The composition of these attached Ag@AgCl core–shell nanoparticles can be easily controlled by adjusting the usage of FeCl₃, resulting in the formation of controllable core–shell nanostructures. Furthermore, these as-prepared graphene oxide–Ag@AgCl nanoparticle composites display effective photodegradation of methylene orange dye under visible light irradiation, which indicates their potential applications in environmental areas.     

Poly(styrene-block-vinylpyrrolidone) beads as a versatile material for simple fabrication of optical nanosensors

A versatile platform for designing optical nanosensors is proposed. The "sensing chemistries" are entrapped into the poly(styrene-block-vinylpyrrolidone) nanobeads having the average size of 245 nm in aqueous media. Addressable staining into the core or the shell of the beads results in nanosensors for essential analytes such as dissolved oxygen, temperature, pH, chloride, and copper ions. Two immobilization procedures are developed: staining in the polystyrene core is performed from a tetrahydrofuran/water mixture (50:50 v/v) and staining in the poly(vinylpyrrolidone) shell is achieved by using the ethanol/water mixture (70:30 v/v). The oxygen and temperature indicators should be preferably immobilized into the core, whereas nanosensors for ions are manufactured by staining into the shell. In the case of the lipophilic pH indicators both procedures result in similar pKa values. The unique properties of the beads make them promising for sensing and imaging even in very complex media, multianalyte sensing, and monitoring of very fast processes.     

Structure characterization of Ag-Ga/poly(methyl methacrylate) nanoparticles

The Ag-Ga/poly(methyl methacrylate) nanoparticles were prepared in-situ by emulsion polymerization method under ultrasonic irradiation without any initiators or metal reductant. HRTEM, EDS and XRD experiments were performed to characterize the nanoparticles. The results indicated that the nanocomposite particles possessed core-shell structure with diameters of 80-200 nm, as well as excellent monodispersity. The phenomenon that the polymer forms the shell via layer-by-layer self-assembly was found. XRD proved the existence of Ag0.72Ga0.28 and the probability of new Ag-Ga alloy because of two unknown diffraction peaks.