模板法制备尖晶石型铁氧体空心纳米球的研究进展

众所周知,铁氧体是一类重要的无机非金属材料,具有熔点高、机械强度高等优势[1]。而具有空心微球结构的铁氧体纳米球还拥有密度小、比表面积大等特点。故尖晶石型铁氧体空心纳米球材料因其在光催化材料、吸波材料、生物医药等领域表现出的优异性能而被广泛研究[2-3]。本文综述了近年来国内外大量用于制备尖晶石型空心结构的铁氧纳米球的方法——模板法。详细介绍了其特点、研究进展及发展趋势。     

无机空心微球制备技术最新进展

无机空心微球由于其特殊的力学、光学、电学等性质及其在催化剂、药物释放和微化学反应器等方面的潜在应用,引起了科研工作者的广泛关注.本文综述了近几年在无机空心微球材料制备方面的最新进展,并对各种制备技术的优缺点进行了分析评价.     

热处理温度对M型BaFe12O19铁氧体空心微球结构和静磁特性的影响

采用共沉淀火焰喷雾工艺合成了M型BaFe12O19铁氧体空心微球。用热重-差热,X射线衍射和扫描电子显微镜表征了产物的结构,并用振动样品磁强计测量了它的静磁性能。结果表明：当热处理温度为800-1100℃,保温3h时,能形成单相M型铁氧体空心微球。随着热处理温度的升高,晶体结构越完整,饱和磁化强度增大,矫顽力减小。     

发泡剂对空心石英玻璃微球结构的影响

空心玻璃微球因具有低密度、高强度、耐高温等优点而被广泛研究。采用喷雾造粒法与粉末法相结合,掺入发泡剂,以射频等离子体作为热源制备空心石英玻璃微球,研究了SiC、CaSO₄、CaCO₃三种发泡剂对制备空心石英玻璃微球的影响。结果表明,通过喷雾造粒法将发泡剂与SiO₂充分混合形成粗坯颗粒,再利用射频等离子设备对粗坯粉末进行高温烧结,得到空心石英玻璃微球。其中CaSO₄、CaCO₃发泡剂效果较差,所产生的气体难以留在玻璃微球内部形成中空气泡;而SiC发泡剂效果最好,在射频等离子烧结过程中产生气体,被玻璃液包裹形成空心结构,得到的玻璃微球平均真密度为1.799 5 g/cm³。选用菲利华石英块状疏松体作为SiO₂原料,当m(SiO₂)∶m(SiC)∶m(H₂O)为100∶3∶300时,可制备出平均真密度为0.72 g/cm³的空心多孔石英玻璃微球。     

低温自反应淬熄法制备微纳米钡铁氧体空心复相陶瓷微珠吸波剂

以Fe(NO3)3-Ba(NO3)2-CO(NH2)2-酚醛树脂-硅烷偶联剂KH550为反应体系,采用低温自反应淬熄法结合热处理工艺,制备了微/纳米钡铁氧体空心复相陶瓷微珠。通过扫描电子显微镜、X射线衍射仪、透射电子显微镜、热分析及高速摄影技术测定了热处理前后微纳米钡铁氧体空心复相陶瓷微珠的形貌、结构及组成,并研究了其形成机理。结果表明:热处理前空心复相陶瓷微珠粒径为0.59至27.1μm,主要为非晶态;热处理后复相陶瓷微珠由六角晶型的Ba3Fe32O51、BaFe12O19和Ba5Fe14O26组成,且表现出片晶与固溶体相互交叉的现象。特殊的试验条件使得团聚粉粒子在火焰场中飞行过程中在受热蓄能阶段、热释放阶段、后燃烧阶段与快速凝固阶段都具有不同的反应机理,从而使得尺寸细化,具有较微米级微珠不同的本征参数。     

以三聚氰胺甲醛微球为模板制备介孔二氧化硅和二氧化钛空心微球

以聚合物三聚氰胺甲醛(MF)微球为模板,十六烷基三甲基溴化铵(CTAB)为致孔剂,经溶胶–凝胶和高温煅烧两步法,制备了SiO2和TiO2介孔结构的空心微球。以亚甲基蓝水溶液为模型物,分别评价了SiO2和TiO2微球的吸附性能和光催化活性。对空心微球的结构、形貌和光谱性质进行了表征。结果表明:两种微球的粒径为300 nm左右,具有完整的球形空腔、较高的比表面积和介孔结构壳层;SiO2空心微球具有良好的吸附性能,而TiO2空心微球在紫外光照射下有高效的光催化活性。     

弱酸性溶液中快速制备PS/SiO_2空心微球及其应用研究

以聚乙烯吡咯烷酮为稳定剂,通过乳液聚合法合成了单分散聚苯乙烯(PS)微球。以PS微球为种子,在弱酸性溶液及不同温度下水解正硅酸乙酯(TEOS),一步合成了具有PS和SiO_2复合壳层的空心微球。研究了溶液p H及反应温度对微球空心度的影响,结果表明,能否得到空心微球受制于不同pH及温度下TEOS水解、缩聚速率以及所生成的纳米Si O_2对PS微球的包覆程度,溶液p H为3.0左右时,室温下反应就可以得到空心微球; p H升高至4.0～5.0时,反应温度达到40℃以上才可以得到空心微球; pH达到6.0时即使升温至50℃以上也无法得到空心微球。通过实验证实了空心SiO_2微球镀层不仅对玻璃具有增透效果,还可以使玻璃表面呈现出超亲水性。     

干凝胶法制备惯性约束聚变靶用大直径空心玻璃微球

为实现惯性约束聚变靶用大直径空心玻璃微球的干凝胶法制备,从数值模拟和工艺实验2个方面研究了发泡剂种类及含量、炉内载气组分、压力和温度对大直径空心玻璃微球制备过程的影响。结果表明:采用碱金属的乙酸盐作为发泡剂可以显著提高干凝胶粒子的发泡效率,提高载气中的氦气含量和升高炉温可以提高干凝胶粒子在吸热阶段的升温速率、更为迅速有效地完成封装过程,从而有利于大直径空心玻璃微球的制备。虽然降低载气压力有利于显著增大空心玻璃微球的直径,但是空心玻璃微球的品质急剧下降。当载气中氦气的体积分数为50%～80%、载气压力为(0.75～1.0)×105Pa、炉温为1500～1700℃时,干凝胶粒子的成球率较高、大直径(700～1000μm)空心玻璃微球的球形度、同心度和表面光洁度较好。     

微/纳米锂锌铁氧体-锌铁氧体空心复相陶瓷微珠的低温自反应淬熄法制备及其电磁损耗性

以Li(NO3)-Zn(NO3)2-Fe(NO3)3-CO(NH2)2-酚醛树脂-KH550为反应配系,采用低温自反应淬熄法,制备了微/纳米锂锌铁氧体-锌铁氧体空心复相陶瓷微珠。通过扫描电子显微镜、X射线衍射、透射电子显微镜、综合热分析、高速摄影技术与矢量网络分析仪分别测定了空心复相陶瓷微珠的本征参数与电磁参数,并研究了其形成机理。结果表明:制备的空心复相陶瓷微珠粒径处于几十纳米至5μm之间,成分由尖晶石型的ZnFe2O4和Fe3O4、四方或立方晶系的Fe2O3、菱面体LiFeO2与立方晶系的Li0.5ZnFe2O45种物相组成,表面形貌呈现出纳米等轴晶、多种形貌的纳米析出晶与非晶形态,其中多种形貌的纳米析出晶与非晶组成共晶结构。制备的空心复相陶瓷微珠在低频段具有良好的磁损耗性。"自身细化"、"自身爆裂"、"碰撞"与"边缘效应"是微/纳米锂锌铁氧体-锌铁氧体空心复相陶瓷微珠形成的主要机理。宽的尺寸分布、表面组织结构多样化以及多种成分构成的复相结构是具有良好的电磁损耗性的原因。     

激光聚变靶用空心玻璃微球制备方法

高质量的空心玻璃微球一直是激光惯性约束聚变实验最广泛采用的靶丸之一,因商用空心玻璃微球的生产方法不能满足实验需要,陆续开发了新的制备方法,如液滴法、干凝胶法、溅射法和降解芯轴技术等.综述了几种方法的制备原理、成球过程、微球产品的特点、在惯性约束聚变实验制靶中的地位以及国内外发展现状等.液滴法制备的微球直径小、壁较薄,干凝胶法制备的微球直径稍大、壁较厚,溅射法主要用于制备阻气层,而降解芯轴技术则将空心玻璃微球产品直径和壁厚范围扩大,所制备的空心玻璃微球是所有制备方法中直径最大和性能最好的.     

Preparation of novel hybrid inorganic–organic hollow microspheres via a self‐template approach

BACKGROUND: Hollow microspheres, especially biodegradable polymeric microspheres, have attracted considerable attention due to their particular characteristics. Up to now, microspheres have been prepared via various strategies, for instance the template synthesis method and the self‐assembly process. However, economic, novel and simple methods to prepare hollow microspheres are still being sought. RESULTS: Phosphazene‐containing microspheres, which contain self‐assembled core‐shell structures, were prepared at high colloid contents using an ultrasonic bath via a self‐template approach. Along with the controlled self‐degradation of the internal core, the corresponding hybrid inorganic–organic hollow microspheres appeared. The mechanism was evidenced by means of transmission and scanning electron microscopy, cross‐polarization with magic angle spinning NMR, Fourier transform infrared spectroscopy, X‐ray diffraction and thermogravimetric analysis. CONCLUSION: It was clarified that the phosphazene‐containing microspheres could be formed and stably dispersed without aggregation even at high colloid contents using the ultrasonic bath method and the microspheres contain self‐assembled core–shell structures. Along with the controlled self‐degradation of the internal core, the corresponding hollow microspheres appeared. The mechanism of this preparation is of great significance because it is completely different from the conventional template synthesis method and the self‐assembly process. The absence of any stabilizing agent and special templates might inspire creative imagination in the design of new morphologies of micro‐ and nanostructures. Copyright © 2007 Society of Chemical Industry     

生物模板法制备磁性中空微球的方法和应用

磁性中空微球在功能性吸附、酶固定化载体、物质的分离纯化、活性物质和药物的封装与控释、靶向给药、污染防治、食品和材料学等领域有突出的应用价值。文章综述了利用生物模板法制备磁性中空微球的制备原理和最新研究成果,并主要分析了软模板法和自模板法两种制备工艺。软模板法工艺主要通过吸附-高温炭化法除去生物模板材料获得固定外形的磁性中空微球。自模板法制备磁性中空微球可依据生物材料自身成分经水热碳化反应或在惰性气体氛围保护下的高温炭化反应生成具有特殊官能团结构的中空碳微球,并将磁性物质溶入或吸附到中空微球中,具体分为水热碳化法和浸渍-高温炭化法;也可将制备好的磁性物质吸附于经过特殊处理过的生物模板材料表面,如吸附-共沉淀法和高温炭化-共沉淀法。总之,生物模板法制备磁性中空微球条件较为温和、无污染,生物模板材料对人体无毒,特别适合于食品、医药等行业的应用,具有很好的生产应用前景。     

Physical and electrochemical characterization of CdS hollow microspheres prepared by a novel template free solution phase method

Novel CdS hollow microspheres have been successfully synthesized via a facile template-free solution-phase reaction from cadmium nitrate and thioacetamide precursors. The morphology of CdS hollow microspheres depends strongly on the ratio between the precursors, cadmium nitrate to thioacetamide ratio. The physical properties of the hollow microspheres have systematically been studied by different characterization methods. The stoichiometry of the hollow microspheres studied by the energy dispersive X-ray diffraction spectroscopy confirmed that the synthesized CdS hollow microspheres are nearly stoichiometric bulk like CdS. The morphology of the hollow microspheres studied by high resolution scanning electron microscopy and transmission electron microscopy observations showed that the CdS hollow microspheres of the size of 2.5 μm have hollow structure and are constructed by several nanoparticles of the size between 30 and 40 nm. The UV-visible diffuse reflectance spectroscopy studies showed that the band gap of the CdS hollow microspheres increased while increasing the cadmium nitrate to thioacetamide ratio. Further electrochemical characterization of CdS hollow microspheres was performed with glassy carbon electrode (GCE) after its chemical modification by CdS dispersed in dimethylformamide. The electrochemical studies showed that with decreasing the band gap energy the electron transfer resistance of CdS/GCE was also found decreased. Moreover, electrochemical impedance spectroscopic measurements showed enhanced DNA adsorption onto CdS/GCE in comparison to GCE. These experiments demonstrate that the CdS hollow microspheres act as an efficient electrode modifier that effectively decreased the charge transfer resistance and capacitance of the modified sensors, which can be used for electroanalytical purposes.     

Preparation of Polycarbonate Hollow Microspheres by Microencapsulation Method

For the purpose of recycling waste polycarbonate (PC) products, PC hollow microspheres were prepared using waste PC products via a microencapsulation method. In the microencapsulation process, dichloromethane was the suitable organic solvent of the oil phase, and the optimal adding amount of gelatin was 1.7 g in 70 g water. The size of the PC hollow microspheres was analyzed by scanning electron microscopy (SEM). The hollow microspheres with mean diameter from 19 to 645 µm could be obtained by varying the preparation factors. The tap density could be controlled through the manipulation of the weight ratio of W₁ and O phase and PC concentration.     

油页岩灰渣制备空心陶瓷微球及机理探讨

以油页岩灰渣为实验原料,利用火焰喷枪熔射法制备了空心陶瓷微球.采用TG-DSC对油页岩灰渣进行热分析,采用SEM和XRD分别对油页岩灰渣和空心陶瓷微球的微观形貌和物相组成进行分析.研究结果表明,利用火焰喷枪熔射法制备的微球绝大多数为球状,极少部分为不规则形状,微球破碎后可发现其为空心结构;空心微球的形成机理为:油页岩灰渣粉末受热熔化、发气物质形成气泡、气泡合并、降温凝固、最终形成空心微球;油页岩灰渣自身疏松的结构、所含充足的发气物质和适宜的熔射温度是形成微球空心结构的重要因素.     

Preparation of phenolic hollow microspheres via in situ polymerization

BACKGROUND: Phenolic hollow microspheres with a closed structure have a set of outstanding thermal characteristics. In the work reported here, a facile method is introduced to fabricate phenolic closed hollow microspheres by in situ polymerization in oil‐in‐water emulsion. Although in situ polymerization has been widely used to prepare hollow microspheres, it has not been utilized for the preparation of phenolic hollow microspheres. RESULTS: The average particle size of the produced microspheres was about 500 µm. Fourier transform infrared spectroscopy indicated that the phenolic microspheres were partially cured during preparation and a significant number of hydroxymethyl groups remained in the microspheres. Thermogravimetric analysis showed that the thermal decomposition temperature of the phenolic hollow microspheres was 420 °C, and residual weight at 800 °C was 62%. Differential thermal analysis showed that the glass transition temperature of the phenolic hollow microspheres was 200 °C. CONCLUSION: Using in situ polymerization, high thermal performance phenolic hollow microspheres are produced. The resultant product possesses a satisfactory closed hollow structure with controlled morphology. Copyright © 2009 Society of Chemical Industry     

Facile fabrication of porous hollow CeO2 microspheres using polystyrene spheres as templates

Porous hollow CeO₂ microspheres were fabricated using negative-charged PS microspheres as templates by a facile method. The hollow CeO₂ microspheres were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and N₂ adsorption?Cdesorption. The results showed that the as-synthesized hollow CeO₂ microspheres are well monodisperse and uniform in size. The porous shells of hollow microspheres are relatively rough and composed of tiny nanoparticles. The external diameter, internal diameter, and shell thickness of hollow CeO₂ microspheres are about 190, 160, and 15?nm, respectively. A possible mechanism for the formation of hollow CeO₂ spheres was also discussed.     

PS/TiO2核壳型微球和空心TiO2微球有序排列的制备

利用纳米级二氧化钛（TiO₂）溶胶微粒与聚苯乙烯（PS）胶体颗粒的混合悬浮液,以垂直共沉积的方法制备了核壳型PS/TiO₂微球的有序排列。当利用煅烧的方法去除PS胶粒晶体模板后,可以形成空心TiO₂微球的三维有序排列。考察了混合悬浮液中两种胶体颗粒的体积比（PS∶TiO₂=R）对空心TiO₂微球有序排列形成的影响。实验结果表明,合适的R值（6∶1）对于空心微球有序排列的形成至关重要。与此同时,浸渍填充法对照实验的结果表明,煅烧过程中TiO₂纳米颗粒晶型转化引起的收缩是造成TiO₂空心球产生的主要原因。     

空心微球的制备及应用进展

对国内外制备空心微球的方法(自组装法,模板法,乳液法等)进行了概述;同时评述了空心微球作为功能材料在不同领域中的最新研究进展。