空心玻璃微球制备技术研究进展

空心玻璃微球（hollow glass microspheres,HGM）是一种新型填料,具有质量轻、强度高、流动性好,隔热、耐腐蚀等优点,在众多领域具有广阔应用前景。目前,已实现产业化的HGM制备技术主要有固相粉末法、液相雾化法和软化学法。本文综述这3种方法制备HGM的基本原理和应用进展,并讨论了各自优缺点,通过对比HGM的性能参数,对不同制备方法存在的问题进行了归纳总结,指出了软化学法制备HGM技术是未来的发展趋势。简要介绍了国内外HGM制备技术的研究现状和发展趋势。未来的研究重点将集中于低能耗、高产率、高强度HGM的制备技术。     

纳米磁性空心微球制备技术研究进展

纳米磁性空心微球由于其独特的结构和性质在国内外引起了越来越多的关注。本文综述了纳米磁性空心微球制备方法的最新研究进展。制备方法一般可分为模板法、非模板法、牺牲模板法、自催化还原法、置换反应法、溶胶-凝胶烧结法和化学镀法。同时,讨论了各种制备方法存在的问题及其优缺点。     

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.     

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。     

逐层自组装法制备纳米二氧化钛空心微球

本文采用溶胶-凝胶法与自组装技术相结合的工艺,以聚乙二醇为模板制备了多层组装的TiO2空心微球。采用TEM对产物进行了表征。以甲基橙溶液的脱色降解率,考察了不同煅烧温度和组装层数对TiO2空心微球光催化性能的影响。结果表明：500℃煅烧下组装四层的TiO2空心微球光催化效果最佳,2h内对甲基橙的催化效果可达到97.25%。     

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。     

靶丸用空心微球制备技术研究进展

激光驱动惯性约束聚变有望解决能源危机,但聚变过程条件的苛刻性对在其中充当靶丸材料的空心微球的品质,如球形度、壁厚均匀性、表面粗糙度、壳层材料密度等提出了严格要求,而制备方法的选择及条件控制直接影响到微球的上述性能。本工作主要综述了研究较为广泛的炉内成球技术、降解芯轴技术以及乳液法的制备过程、适用范围、优劣势等,并对乳液法的形成机理和影响因素进行了较详细的阐释。     

水热界面反应制备二氧化钛空心微球

采用水热法,在油酸/水/乙醇体系中,钛酸四丁酯前驱体分解团聚得到具有空心结构的TiO2微球。利用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附脱附(BET)对样品进行表征,并通过对甲基橙的紫外光催化降解评价样品的光催化性能。结果表明该空心微球为锐钛相,粒径约为1～2μm,随着时间的延长其结晶性增强。BET结果显示该空心微球具有较大的比表面积300.20m2.g-1,内部颗粒之间形成介孔结构。利用SEM研究了该空心微球的生长特点和生长机理,结果表明钛酸四丁酯在油水界面反生分解缩聚反应,然后经过由内向外的Ostwald ripening(OR)过程得到空心微球,通过调节水油的比例可以调控微球的形貌和粒径。光催化性能测试表明这种空心微球结构的TiO2材料具有较高的催化活性。     

空心玻璃微球化学镀镍研究

研究了先偶联、再活化的前处理工艺；分别考察了1．6、2．4、3．2、4．0、4．8g的5种装载量时磁性微球的形貌；对前处理过的微球进行化学镀镍得到镍包覆空心玻璃微球，分别使用扫描电镜、X射线能谱仪和X射线衍射仪对镍镀层的形貌结构、成分和晶体结构进行了表征。研究表明，偶联处理有助于空心玻璃微球在活化过程中吸附钯，使活化微球中钯的摩尔分数从0提高到0．1053％。控制装载量为2．4～4．0g/L，可以得到包覆完整、均匀的镍镀层；镀层的主要成分是Ni，其摩尔分数为98．2174％；镀层Ni的晶体结构为面心立方结构，与单质镍相似.     

含莫来石相的空心陶瓷微球制备

以硅酸钠、氧化铝粉为原料,尿素为发泡剂,通过造粒、除钠、高温烧结等工艺制备直径500～1000μm、壁厚50～60μm的空心陶瓷微球。分析了除钠对空心微球元素组成的影响,以及除钠与未除钠的空心陶瓷球1500℃高温烧结后的相组成区别,结果表明除钠效果是十分明显的。     

开口空心ZnS/CdS纳米微球的制备、表征及其光降解亚甲基蓝性能

采用非均相回流技术制备开口空心ZnS/CdS纳米微球,利用TEM和XRD对样品进行表征与分析,通过降解亚甲基蓝溶液和正交设计试验考察各影响因素。结果表明,催化剂用量是影响光降解亚甲基蓝的主要因素,在催化剂用量70 mg、m(ZnS)∶m(CdS)=1∶3和避光搅拌时间30 min条件下,浓度10 mg·L^-1的亚甲基蓝溶液降解率达91.34%。     

Preparation of hollow poly(imino ether ketone) microspheres by microliquid technique

1, 4‐bis (4‐amiophenoxy) benzene and 1, 4‐Bis (4‐bromobenzoyl) benzene as monomers, poly(imino ether ketone) (PIEK) was synthesized via palladium‐catalyzed aryl amination reaction. Based on the good chemical and physical properties, big diameter (0.6–2 mm) hollow microspheres of PIEK, used for Inertial Confinement Fusion research, were prepared by using the microliquid technique and double‐layer latex technique. A new double T‐channel droplet generator was designed and developed for fabrication of controlled‐size PIEK hollow microspheres continuously. Study on manipulative condition of diameter and thickness of microspheres was done, and density matching impacting on the quality of shells was discussed. The structures of the PIEK hollow microspheres were characterized, and they possessed equal wall thickness and good spherical symmetry. The properties of the microspheres were detected, and the results showed that they showed good stability under cold environment and high temperature. Additionally, the PIEK hollow microspheres exhibited good mechanical and anti‐irradiation properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of the stimuli-responsive ZnS/PNIPAM hollow spheres

Novel quantum dots ZnS/poly(N-isopropylacrylamide) (PNIPAM) hybrid hollow spheres were obtained by localizing free radical polymerization of NIPAM and crosslinker (MBA) at the peripheral of PCL nanoparticles, followed by biodegradation of PCL with an enzyme of the Lipase PS. The formation of ZnS/PNIPAM hollow spherical structures and the thermo-sensitive reversible properties was systematically investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS), respectively. The ZnS/PNIPAM hollow spheres possess the photoluminescence properties and a swelling and de-swelling at about 32 °C, which agrees well with the slight red shift in photoluminescence spectra.     

碳酸钙中空微球的制备及机理

采用沉淀反应方法,利用聚乙烯吡咯烷酮(PVP)和十二烷基磺酸钠(SDS)复合添加剂作为有机模板,制备了中空球状方解石型碳酸钙,同时考察了不同温度、SDS和PVP浓度对碳酸钙结晶和聚集行为的影响,进而对其反应机理进行了初步探讨。     

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     

Preparation of hollow alumina microspheres by microwave-induced plasma pyrolysis of atomized precursor solution

Hollow alumina microspheres have been prepared by microwave-induced (MI) plasma pyrolysis of atomized aerosols of precursor solutions and subsequent calcination at 1300 °C for 2 h. When an aqueous solution of 0.5 mol dm⁻³ Al(NO₃)₃ without any additives was used as a precursor, hollow -Al₂O₃ microspheres with a thick shell wall were prepared after post-calcination at 1300 °C. The addition of a polypropylene (PO)–polyethylene(EO) blockcopolymer (molecular weight: 2900–6500) to the precursor solution was effective for increasing the yield of hollow microspheres, but resulted in the formation of many cracks and holes in the thinned shell wall. Hollow alumina microspheres with a thin, but strong, shell layer could be prepared by the simultaneous addition of tetraethylorthosilicate.     

铁掺杂二氧化钛空心球的制备及性能

以TiF₄为钛源、九水合硝酸铁为掺杂前体,采用水热法制备铁掺杂的TiO₂空心微球。采用SEM、TEM、XRD、BET、XPS等技术对样品的形貌、结构、晶型、比表面积、元素组成等进行表征,以亚甲基蓝（MB）的光催化降解为目标反应,评价其光催化活性。结果表明,160℃下水热反应生成的纳米TiO₂空心微球晶型为锐钛矿,少量掺铁并不影响微球的形貌及晶体结构。光催化实验表明,160℃下水热反应12 h生成的TiO₂空心微球样品均匀性好、光催化活性最佳;铁掺杂能显著提高TiO₂空心微球的催化活性,当铁钛比为1.5:100时,所得样品粒径最小,比表面积最大,光催化活性最高。     

PS-PVA-CH塑料空心微球充D2

研究了激光惯性约束聚变靶用PS-PVA-CH三层塑料空心微球采用热扩散法高温高压充氘气技术。实验研究表明,对于直径300 μm、PS壁厚5～7 μm、PVA壁厚3～5 μm、CH层厚4～6 μm的塑料微球,50℃充气的平衡时间为20～40 h,70℃的平衡时间为7～12 h,90℃的平衡时间为2～4 h。在室温25℃时,微球的气体渗透系数为（3.0～4.2）×10^-19 mol·m^-1·s^-1·Pa^-1,对应的保气半寿命为28～37 h。对于参数接近的微球,如果充气时间相同,充气外压与微球内压基本呈正比。当外压达到6.0 MPa时微球开始出现破损。     

Preparation of hollow magnetite microspheres and their applications as drugs carriers

ABSTRACT: Hollow magnetite microspheres have been synthesized by a simple process through a template-free hydrothermal approach. Hollow microspheres were surface modified by coating with a silica nanolayer. Pristine and modified hollow microparticles were characterized by field-emission electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, FT-IR and Raman spectroscopy, and VSM magnetometry. The potential application of the modified hollow magnetite microspheres as a drug carrier was evaluated by using Rhodamine B and methotrexate as model drugs. The loading and release kinetics of both molecules showed a clear pH and temperature dependent profile. GRAPHICAL ABSTRACT: Hollow magnetite microspheres have been synthesized. Load-release experiments with Rhodamine-B as a model drug and with Methotrexate (chemotherapy drug used in treating certain types of cancer) demonstrated the potential applications of these nanostructures in biomedical applications.     

介孔中空二氧化硅微球制备及吸附缓释性能研究

以用分散聚合法制得的不同粒径单分散阳离子型聚苯乙烯球为模板、十二胺为表面活性剂,通过溶胶-凝胶方法,在模板上包裹二氧化硅壳,并通过浸渍和焙烧制备了具有介孔结构的中空二氧化硅微球.TEM,SEM显示微球具有很好的单分散性和中空结构.小角XRD表明球壳上具有六方介孔结构.实验表明控制模板粒子大小可改变介孔中空二氧化硅微球粒径,改变正硅酸乙酯浓度可以调整二氧化硅球壳厚度.通过对丁基罗丹明B染料的吸附装载与释放实验证实了其有很好的渗透性和缓释性能.