气凝胶微球的制备和应用

与传统的块状气凝胶不同,气凝胶微球是一种具有独特结构的新材料。它既由纳米级材料构建,又有微米级尺寸,同时还具备气凝胶特有的热、声、光、电性质和复杂的三维网络拓扑结构,在生物医药、环境修复、功能性载体、能源存储和转化等领域具有广泛的应用潜力。近年来,国内外关于气凝胶微球的研究进展迅速,但关于气凝胶微球的综述还没有报道。本文结合气凝胶微球领域最新的研究进展,从气凝胶微球的制备方法、种类以及不同种类的气凝胶微球在环境、医药、能源领域的应用等方面进行了综述。     

回流沉淀聚合:单分散聚合物纳米水凝胶微球制备新技术

针对高效制备单分散聚合物纳米水凝胶微球手段欠缺问题,我们发展了一种新型的纳米水凝胶微球制备新技术——回流沉淀聚合技术,与以往的沉淀聚合及蒸馏沉淀聚合相比,该方法效率更高、普适性更强、操作更简单,适合高效制备单分散的纳米水凝胶微球及其复合微球.通过考察制备聚甲基丙烯酸微球过程中的反应时间、固含量、交联剂含量、混合溶剂比例等影响因素,成功制备了形态可控、尺寸均一、水中分散性良好的聚甲基丙烯酸纳米水凝胶微球,并给出了微球形态控制的基本规律.通过该技术制备的纳米水凝胶微球及其复合微球将被广泛用于生物医用材料中.     

TiO2/SiO2气凝胶微球的制备及其表征

以TiOSO4和硅溶胶为原料, 加入甲酰胺作为干燥控制化学添加剂, 采用W/O乳状液中的溶胶-凝胶法制备TiO2/SiO2凝胶微球, 通过正硅酸乙酯母液浸泡、溶剂交换、陈化和常压干燥技术制备TiO2/SiO2气凝胶微球, 采用光学显微镜、SEM、TEM和BET比表面及孔分布测定等手段对所得样品进行表征. 典型的气凝胶微球样品是由粒径15 nm左右, 粒度分布相当均匀的球状纳米粒子构成的轻质纳米多孔材料, 表观密度为177 kg•m-3, 比表面积372 m2•g-1, 平均孔径22.78 nm, 孔隙率高达92.0％, 微球的宏观粒径为50 m. 依据制备条件的变化, TiO2/SiO2气凝胶微球的宏观粒径可控在10～200 m之间, 表观密度为150～300 kg•m-3, 比表面积为300～400 m2•g-1, 平均孔径在18.71～22.78 nm之间变化.     

以微凝胶为基质的杂化材料制备及应用研究进展

水凝胶微球即尺寸较小的球形水凝胶,除了凝胶特性外,其特点主要是具有较小的尺寸和球形形貌。由于其网络结构和快速的刺激响应性,使其作为模板制备具有独特性能的杂化材料而备受关注。本文主要从几个方面阐述了以微凝胶为基质制备杂化材料的方法及其应用。包括了磁性金属氧化物-凝胶杂化材料、金属单质-凝胶杂化材料、生物活性-凝胶杂化材料及功能化的球形和膜状杂化材料,最后介绍了本实验室以微凝胶为基质制备表面图案化杂化材料的方法。     

新颖表面结构的脲醛树脂-聚丙烯酰胺复合微球的制备研究

将高分子微凝胶模板法应用于制备脲醛树脂[Urea-formaldehyde resin (UF Resin)]-聚丙烯酰胺[Polyacrylamide (PAM)]有机-有机复合微球材料. 以PAM高分子微凝胶为模板, 通过控制甲醛和尿素的缩聚反应在反相悬浮体系中进行, 制备得到了具有新颖表面形貌的脲醛树脂-聚丙烯酰胺[UF Resin/PAM]有机-有机复合微球, 利用扫描电子显微镜(SEM)、热重分析(TGA)、红外(FT-IR)等手段对复合微球进行了表征. 实验结果表明, 复合微球的表面形貌与甲醛和尿素溶液的pH值、甲醛和尿素溶液的浓度、甲醛和尿素的摩尔比、模板的组成等因素有关. 可以预期, 本研究方法将为制备具有特异表面形貌的有机-有机复合微球材料提供了一条有效的途径.     

磁性壳聚糖硅胶复合微球的制备及其吸附Cu~(2+)的性能研究

以壳聚糖与正硅酸四乙酯为原料,采用溶胶-凝胶法,用戊二醛辅助交联合成了磁性壳聚糖硅胶复合微球。通过红外光谱、扫描电镜、X-射线衍射等方法对磁性壳聚糖硅胶复合微球的形态和组成特性进行分析,制备的磁性复合微球中壳聚糖与硅胶材料复合均匀,材料粒径均一,机械强度较高。考察了制备的磁性壳聚糖硅胶复合微球对Cu~(2+)的吸附性能,结果表明微球对Cu~(2+)具有较好的吸附性能,吸附容量达到98.7mg/g。     

纳米结构型PMAA/CdS复合微球的微凝胶模板法制备研究

以微凝胶为模板,利用微凝胶三维网络结构对无机沉积反应的限域和导向作用,制备了具有核-壳结构的聚甲基丙烯酸/硫化镉(PMAA/CdS)有机/无机复合微球材料.复合微球的制备包含两个基本步骤首先,以反相乳液聚合法得到包含Cd(Ac)2的聚甲基丙烯酸微凝胶;然后,在搅拌过程中向反应体系中缓慢通人H2S气体,使镉离子沉积为CdS,经洗涤处理后得到PMAA/CdS复合微球.SEM观察表明,复合微球表面呈现均一的微纳米结构,这种结构可因微球制备条件的不同而不同.而且,超声处理可使微球表面趋于光滑.X射线衍射分析表明复合微球中CdS处于晶态,具有立方结构.此外,复合微球因CdS的存在而具有光致发光特性.     

磺化聚苯乙烯纳米微球-聚丙烯酰胺杂化水凝胶的制备及性能

首先通过乳液聚合法合成了聚苯乙烯(PS)微球,该微球经浓硫酸磺化后得到了磺化聚苯乙烯(SPS)微球;然后将合成的SPS微球作为多功能交联点加入丙稀酰胺(AAm)化学水凝胶网络中制备了SPS-PAAm杂化水凝胶。通过扫描电镜、透射电镜观察了SPS微球及杂化水凝胶的微观结构。研究了SPS微球对SPS-PAAm杂化水凝胶的凝胶分数、溶胀性能和力学性能的影响。结果显示:随着SPS微球用量的增加,SPS-PAAm水凝胶的凝胶分数先增加后降低,平衡溶胀度降低;SPS微球的加入能改善水凝胶的力学性能,随着SPS含量的增加,水凝胶的拉伸强度和能量损耗增加;SPS微球和PAAm分子链间存在物理相互作用。     

聚合物纳米微球增韧水凝胶的制备与表征

通过无皂乳液聚合制备阳离子纳米微球(NPs),并将其作为疏水交联中心来制备高强韧水凝胶。体系中的疏水单体甲基丙烯酸月桂酯(LMA)在表面活性剂作用下聚集到纳米微球表面,形成疏水缔合中心,通过原位引发自由基聚合得到纳米微球杂化的聚丙烯酰胺疏水缔合水凝胶P(AAm-LMA)-NPs。当凝胶受到应力时,由纳米微球形成的动态交联点通过断裂与重组可以有效地耗散能量,极大地提高了凝胶的强度和韧性。因此,所制备的P(AAm-LMA)-NPs水凝胶表现出十分优异的机械性能,其最大拉伸强度可达860 kPa,断裂伸长率为1280%,断裂韧性为3.8 MJ/m³。聚合物纳米微球增韧水凝胶的力学性能优异,有望在生物医学和工业领域有重要应用。     

硫化物-高分子复合微球表面形貌与模板组成关系的研究

以N-异丙基丙烯酰胺(NIPAM)和甲基丙烯酸(MAA)为单体, 通过反相悬浮聚合法制备了多种MAA含量不同的阴离子型P(NIPAM-co-MAA)共聚微凝胶. 以这些共聚微凝胶为模板, 在不同表面活性剂存在下, 合成了一系列CuS(CdS、ZnS)-P(NIPAM-co-MAA)无机-有机复合微球材料, 研究了表面活性剂种类, 模板组成等因素对上述硫化物-高分子复合微球表面形貌的影响. 结果表明, 实验条件下所得复合微球表面均具有图案化结构, 该结构明显依赖于表面活性剂的种类和模板微凝胶的组成. 就模型体系而言, 随表面活性剂Span-20、Span-80和Span-85的HLB(亲水亲油平衡)值降低, 微球表面形貌趋于粗糙, 但仍然十分规整; 就模板组成而言, 模板中MAA含量增加使得复合微球的表面形貌变得更加精细. 据此, 认为通过选用合适的表面活性剂和微凝胶模板可以在一定范围内调控这些无机-有机复合微球的表面形貌, 从而为后续应用研究奠定基础.     

Uniform biodegradable hydrogel microspheres fabricated by a surfactant-free electric-field-assisted method

Uniform biodegradable hydrogel microspheres (HMS) with precisely controlled size have been fabricated using an electric-field-assisted precision particle fabrication technique. Particle agglomeration was prevented by charging the hydrogel drops and allowing Coulomb repulsion to separate them. As a result, surfactant-free and non-toxic particle fabrication was possible and the resulting microspheres were most suitable for biomedical and food-related applications. Due to the size uniformity, the present HMS may serve as a convenient yet most accurate vehicle for controlled delivery of therapeutic agents and other active ingredients.     

Aerogel microspheres based on cellulose nanofibrils as potential cell culture scaffolds

Crosslinked poly(vinyl alcohol) (PVA)/cellulose nanofibril (CNF) hybrid aerogel micro-spheres with two different particle sizes were fabricated via a combination of the water-in-oil (W/O) emulsification process and the freeze-drying process. The aerogel micro-spheres were highly porous with a bulk density as low as 0.0047 g/cm³ for the large microspheres. The pore size of the microspheres ranged from nano- to micro-meters. Preliminary biocompatibility assays of the aerogel microspheres were investigated with NIH 3T3 cells to explore their potential application as cell culture scaffolds. The highly crosslinked aerogel microspheres were robust and were able to maintain their shape during the cell culture process. The live/dead assay showed that the cells could be seeded, attached, and proliferated on the surface of PVA/CNF aerogel microspheres. The fluorescence images showed that some of the cells migrated into the inner pores of the microspheres. Moreover, the large microspheres with larger average pore sizes had a higher cell count than that of the small microspheres. This study confirms that the PVA/CNF aerogel microspheres fabricated in this work are nontoxic and biocompatible. Furthermore, the interconnected, highly porous nanofibrous structure of the microspheres can successfully facilitate cell attachment, differentiation, and proliferation.     

Chitosan Bio‐Based Organic–Inorganic Hybrid Aerogel Microspheres

Recently, organic–inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface‐reactive organic–inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self‐standing microspheres. Nanocasting of sol–gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO₂ supercritical drying provide high‐surface‐area organic–inorganic hybrid materials. Examples including chitosan–SiO₂, chitosan–TiO₂, chitosan–redox‐clusters and chitosan–clay‐aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption.     

Advances in fabrication of emulsions with enhanced functionality using structural design principles

Emulsion science and technology has been used for many years to create a diverse range of commercial products, including pharmaceuticals, foods, agrochemicals, lubricants, personal care products, and cosmetics. The majority of these products are conventional emulsions consisting of droplets of one liquid dispersed in another immiscible liquid, e.g., oil-in-water emulsions. Recently, there has been growing interest in extending the functional performance of emulsion-based products using structural design principles. This article reviews recent developments in the creation of structured emulsions, including multiple emulsions, multilayer emulsions, colloidosomes, microclusters, filled hydrogel microspheres, and hybrid systems. The structure, fabrication, properties, and potential applications of each type of structured emulsion are discussed. In addition, recent advances in the fabrication of emulsion droplets with specific properties (size, charge, interfacial properties, and physical state) are also reviewed, since these are the basic building blocks of structured emulsions.     

Aerogel: Space exploration applications

The unique physical properties of aerogel have proven to be enabling to a variety of both flight and proposed space exploration missions. The extremely low density and highly porous nature of aerogel makes it suitable for stopping high velocity particles, as a highly efficient thermal barrier, and as a porous medium for the containment of cryogenic fluids. The use of silica aerogel as a hypervelocity particle capture and return media for the Stardust Mission has drawn the attention of many in the space exploration community. Aerogel is currently being used as the thermal insulation material in the 2003 Mars Exploration Rovers. The SCIM (Sample Collection for the Investigation of Mars) and the STEP (Satellite Test of the Equivalence Principle) Missions are both proposed space exploration missions, in which, the use of aerogel is critical to their overall design and success. Composite materials comprised of silica aerogel and oxide powders are under development for use in a new generation of thermoelectric devices that are planned for use in many future space exploration mission designs. Work is currently ongoing in the development and production of non-silicate and composite aerogels to extend the range of useful applications envisioned for aerogel in future space exploration projects.     

Facile Assembly of Graphene on Anion Exchange Resin Microspheres for Electrochemical Sensing and Biosensing

Graphene sheets were assembled on anion exchange resin (AER) microspheres based on the electrostatic interactions between graphene oxide and AER and subsequent chemical reduction. The prepared graphene‐coated AER microspheres were characterized by scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared spectroscopy. They were then embedded in the bores of pipette tips to fabricate disposable electrodes for electrochemical sensing. The workability and performance of the novel electrodes were examined by analyzing the electrochemical behavior of the electrodes for the sensing of ascorbic acid, dopamine, uric acid, acetaminophen, aniline, and glucose by cyclic voltammetry and amperometry. The advantages of the electrodes include ease of fabrication, low cost, pronounced electrocatalytic activity, and rapid response. Thus, they hold great promise for a wide range of applications.     

高力学强度细菌纤维素气凝胶纤维的连续化制备

气凝胶纤维因其高外表面积和高柔韧性在能量管理系统中具有潜在应用而引起了广泛关注.但是,目前制备的气凝胶纤维力学强度较低,限制了其实际应用.为提高气凝胶纤维力学性能,在始终保持细菌纤维素(BC)纳米纤维处于湿态下,利用NaOH/尿素/硫脲复合溶剂直接低温溶解原生BC,获得透明的BC纺丝原液;通过湿法纺丝制备了BC水凝胶纤维,经过水洗和冷冻干燥后处理,制得BC气凝胶纤维.采用偏光显微镜(POM)、13C核磁共振(13C-NMR)和高级旋转流变仪研究BC在复合溶剂中的溶解过程与状态;利用全反射傅里叶变换红外吸收光谱(ATR-FTIR)、X射线衍射(XRD)和热失重(TG)研究BC溶解前后结构与性能变化;利用场发射扫描电镜(FESEM)、全自动比表面积和孔径分布分析仪、单丝强力仪对获得的BC气凝胶纤维结构与性能进行表征.结果表明,复合溶剂在?15℃条件下可以直接溶解原生湿态BC,最高溶解浓度为3 wt%;采用湿法纺丝制得高度多孔的连续BC气凝胶纤维,比表面积高达192 m^2/g且具有优异的力学性能,断裂强度和杨氏模量高达(9.36±1.68)MPa和(176±17.55)MPa,如0.4 mg BC气凝胶纤维可以支撑高于其本身质量5×10^4倍的重物.     

Sol–gel development activities at IGCAR,Kalpakkam

Sol–gel based fuel fabrication processes have the potential to be the nuclear fuel fabrication processes in the future. Hence development of sol–gel technology for nuclear fuel fabrication is being the pursued in the Department of Atomic Energy in India. As a part of the efforts, a laboratory scale facility for fabrication of test fuel pins for irradiation in the Fast Breeder Reactor (FBTR), Kalpakkam has been set up at the Indira Gandhi Centre for Atomic Research, Kalpakkam, India. These fuel pins will be vibropacked with sol–gel derived microspheres or stacked with pellets obtained by compaction of sol–gel derived microspheres. The facility is aimed at demonstration of the remote operation of the fuel pin fabrication process through the sol–gel route. A capsule containing three test pins from this facility will be irradiated in FBTR. The design features of the facility and the test fuel pins are described in this paper.