Self-assembly patterning of colloidal crystals constructed from opal structure or NaCl structure

We developed a novel self-assembly process to fabricate an orderly array of particle wires constructed from a close-packed colloidal crystal without preparation of patterned templates. A substrate was immersed vertically into a SiO2 colloidal solution, and the liquid surface moved downward upon evaporation of solution. Particles formed a mono-/multiparticle layer, which was cut by the periodic drop-off of solution. The orderly array of particle wires was successfully fabricated, showing the suitability of the self-assembly process for the fabrication of nano-/microstructures constructed from nano-/microparticles or blocks. The mechanism of the assembly process and control of thickness, width, and interval of particle wires were further discussed. Moreover, an array of particle wires constructed not from close-packed face-centered cubic (or hexagonal close packed) structure but from two kinds of particles was realized to fabricate an array of particle wires with NaCl structure by this self-assembly process.     

熵驱大分子胶体粒子的柱状受限结晶

熵是物理化学的基本状态参量,在统计力学和热力学中处于核心位置.按照玻尔兹曼的微观解释,熵可以由孤立系统微观状态的数目(W)给出,即S=kBlnW,这里kB为玻尔兹曼常数[1,2].根据此公式,微观状态数越多,系统越混乱,熵越大,所以熵常被视作体系无序程度的度量.但熵增仅对应体系微观状态数的增加,与可观测的结构有序程度无关[3~5].在一些典型的软物质体系中,结构越有序熵反而越大,如胶体硬球在随机密堆积点的有序结晶[6]及描述各向异性棒状分子从各向同性相到向列相转变的Onsager原理[7].     

Purification and stabilization of colloidal ZnO nanoparticles in methanol

Purification and stabilization of colloidal ZnO nanoparticles synthesized from zinc acetate dihydrate and potassium hydroxide in methanol have been performed. Isopropanol and hexane were utilized to achieve the precipitation-redispersion washing procedure in methanol. The results from atomic absorption spectroscopy show that the concentration of K⁺ cation can be dramatically reduced by washing. X-ray diffraction and transmission electron microscopy results show that zinc layered double hydroxide formed in the ZnO precipitate can be effectively removed through concentrating the unpurified ZnO colloids by solvent evaporation. The purified ZnO nanoparticles can be fully redispersed in methanol, but become unstable with time due to the low concentration of acetate in the colloids. Fortunately, the unstable ZnO methanol colloids are found to become stable after addition of a small amount of hexane. The present study is of particular significance for the preparation of purified colloidal ZnO nanoparticles for device fabrication, functional ZnO coatings and polymer nanocomposite applications.     

Highly luminescent lead sulfide nanocrystals in organic solvents and water through ligand exchange with poly(acrylic acid)

Hydrophobic lead sulfide quantum dots (PbS/OA) synthesized in the presence of oleic acid were transferred from nonpolar organic solvents to polar solvents such as alcohols and water by a simple ligand exchange with poly(acrylic acid) (PAA). Ligand exchange took place rapidly at room temperature When a colloidal solution of PbS/OA in tetrahydrofuran (THF) was treated with excess PAA, the PbS/PAA nanocrystals that formed were insoluble in hexane and toluene but could be dissolved in methanol or water, where they formed colloidal solutions that were stable for months. Ligand exchange was accompanied by a small blue shift in the band-edge absorption, consistent with a small reduction in particle size. While there was a decrease in quantum yield associated with ligand exchange and transfer to polar solvents, as is commonly found for colloidal quantum dots, the quantum yields determined were impressively high: PbS/OA in toluene (82%) and in THF (58%); PbS/PAA in THF (42%) and in water (24%). The quantum yields for the PbS/PAA solutions decreased over time as the solutions were allowed to age in the presence of air.     

Bulk synthesis of polymer-inorganic colloidal clusters

We describe a procedure to synthesize colloidal clusters with polyhedral morphologies in high yield (liter quantities at up to 70% purity) using a combination of emulsion polymerization and inorganic surface chemistry. We show that the synthesis initially used for silica-polystyrene hybrid clusters can be generalized to create clusters from other inorganic and polymer particles. We also show that high yields of particular morphologies can be obtained by precise control of the inorganic seed particle size, a finding that can be explained using a hard-sphere packing model. These clusters can be further chemically modified for a variety of applications. Introducing a cross-linker leads to colloidal clusters that can be index matched in an appropriate solvent, allowing them to be used for particle tracking or optical studies of colloidal self-assembly. Also, depositing a thin silica layer on these colloids allows the surface properties to be controlled using silane chemistry.     

Particle and substrate charge effects on colloidal self-assembly in a sessile drop

By direct video monitoring of dynamic colloidal self-assembly during solvent evaporation in a sessile drop, we investigated the effect of surface charge on the ordering of colloidal spheres. The in situ observations revealed that the interaction between charged colloidal spheres and substrates affects the mobility of colloidal spheres during convective self-assembly, playing an important role in the colloidal crystal growth process. Both ordered and disordered growth was observed depending on different chemical conditions mediated by surface charge and surfactant additions to the sessile drop system. These different self-assembly behaviors were explained by the Coulombic and hydrophobic interactions between surface-charged colloidal spheres and substrates.     

Spontaneous formation of cluster array of gold particles by convective self-assembly

Cluster arrays composed of metal nanoparticles are promising for application in sensing devices because of their interesting surface plasmon characteristics. Herein, we report the spontaneous formation of cluster arrays of gold colloids on flat substrates by vertical-deposition convective self-assembly. In this technique, under controlled temperature, a hydrophilic substrate is vertically immersed in a colloid suspension. Cluster arrays form when the particle concentration is extremely low (in the order of 10(-6)-10(-8) v/v). These arrays are arranged in a hierarchically ordered structure, where the particles form clusters that are deposited at a certain separation distance from each other, to form "dotted" lines that are in turn aligned with a constant spacing. The size of the cluster can be controlled by varying the particle concentration and temperature while an equal separation distance is maintained between the lines formed by the clusters. Our technique thus demonstrates a one-step, template-free fabrication method for cluster arrays. In addition, through the direct observation of the assembly process, the spacing between the dotted lines is found to result from the "stick-and-slip" behavior of the meniscus tip, which is entirely different from the formation processes observed for the striped patterns, which we reported previously at higher particle concentrations. The difference in the meniscus behavior possibly comes from the difference in colloidal morphology at the meniscus tip. These results demonstrate the self-regulating characteristics of the convective self-assembly process to produce colloidal patterns, whose structure depends on particle concentration and temperature.     

Fabrication of colloidal grid network by two-step convective self-assembly

We explored a "template-free" approach to arranging colloidal particles into a network pattern by a convective self-assembly technique. In this approach, which we call "two-step convective self-assembly," a stripe pattern of colloidal particles is first prepared on a substrate by immersing it in a suspension. The substrate with the stripes is then rotated by 90° and again immersed in the suspension to produce stripes perpendicular to the first ones, resulting in a grid-pattern network of colloidal arrays. The width of the colloidal grid lines can be controlled by changing the particle concentration while maintaining an almost constant spacing between the lines. On the basis of these results, we propose a mechanism for grid pattern formation. Our method is applicable to various types of particles. In addition, the wide applicability of this method was employed to create a hybrid grid pattern.     

水—正己烷—甲醇体系的液液平衡研究

随着国民经济的发展 ,汽油、柴油等发动机燃料的供求关系会日趋紧张 ,寻求代用燃料是今后燃料工业发展的必然趋势 ,而以甲醇、乙醇等作为部分代用燃料成分是今后的一个重要方向[1] 。由于传统的甲醇合成工艺受到传热、传质和化学平衡的限制 ,原料及能源的利用率有待于进一步提高。钟炳等人根据超临界相反应特点 ,向体系中加入适宜溶剂如正己烷 ,在超临界条件下合成甲醇 ,同时克服了现有过程存在的热力学限制和传热限制 ,并将ＣＯ单程转化率提高到 90 %以上[2 ] 。但是 ,正己烷的加入给合成甲醇过程带来了产物分离和溶剂回收问题。反应器流出…     

Collodial cluster arrays by electrohydrodynamic printing

A "stable" electrohydrodynamic jet is used to print arrays of colloidal suspensions on hydrophobic surfaces. Printed lines break up into sessile drops, and capillary forces guide the self-assembly of colloidal particles during the evaporation of the liquid, resulting in arrays of colloidal single particles or particle clusters depending on the concentration of the suspensions. The clusters differ from those formed in the absence of a substrate when the number of particles is larger than three. Multiple structures are found for the same number of particles.     

Microwave-Assisted Self-Organization of Colloidal Particles Inside Water-in-Oil Emulsions

Commercial amidine polystyrene microspheres were self-organized to obtain colloidal microclusters from water-in-oil emulsion droplets as confining geometries. For demulsification process, microwave was irradiated to remove water droplets selectively resulting in the shrinkage of water droplets which induces inward capillary pressure for the particle self-assembly. The amidine polystyrene clusters were coated with silica nanospheres or titania nanoparticles by co-organizing the mixed particle suspensions inside water droplets by microwave heating. Titania-coated polystyrene clusters were calcined to produce hollow macroporous titania powders. Finally, sulfate-coated polystyrene microspheres were self-assembled with silica nanoparticles to generate polystyrene/silica composite clusters by microwave irradiation method.     

In situ observation and measurement of evaporation-induced self-assembly under controlled pressure and temperature

In situ observations of evaporation-induced colloidal self-assembly and in situ measurement of mass transfer process were carried out under a temperature and pressure controlling system. The growth processes of colloidal crystals in different cuvettes recorded by direct video observations revealed that solvent flow around the pore space of the crystal played a key role. By changing the circumstances (temperature and pressure) of the self-assembly system and properties of fluid (viscosity), different evaporation rate of solvent and growth rate of colloidal crystals were measured directly. It turned out that both evaporation rate and growth rate as functions of temperature and pressure fit Stefan's law well. Furthermore, the transfer process of particles in the fluid flow was determined by the fluid-dynamic characteristics, which can be analyzed by the Reynolds number. The results obtained provide an insight into the growth mechanisms of self-assembly and theoretical basis for optimizing the experimental growth conditions of colloidal crystals.     

Hamaker constants of iron oxide nanoparticles

The Hamaker constants for iron oxide nanoparticles in various media have been calculated using Lifshitz theory. Expressions for the dielectric responses of three iron oxide phases (magnetite, maghemite, and hematite) were derived from recently published optical data. The nonretarded Hamaker constants for the iron oxide nanoparticles interacting across water, A(1w1) = 33 - 39 zJ, correlate relatively well with previous reports, whereas the calculated values in nonpolar solvents (hexane and toluene), A(131) = 9 - 29 zJ, are much lower than the previous estimates, particularly for magnetite. The magnitude of van der Waals interactions varies significantly between the studied phases (magnetite < maghemite < hematite), which highlights the importance of a thorough characterization of the particles. The contribution of magnetic dispersion interactions for particle sizes in the superparamagnetic regime was found to be negligible. Previous conjectures related to colloidal stability and self-assembly have been revisited on the basis of the new Lifshitz values of the Hamaker constants.     

乳胶颗粒与硝基重氮树脂的自组装

高分子通过静电、氢键、电荷转移等的自组装 ,尤其是静电自组装已有大量报道[1] .带重氮基(Ｎ+2 )高分子 (重氮树脂 ,ＤＲ)自组装的特点是形成组装膜的弱键 ,光照下能转变为共价键 ,不稳定的膜变成稳定的膜[2 ] .乳胶颗粒的组装 ,因胶体晶体、光子晶体的进展 ,越来越受关注[3 ] ,国内也有一些评述文章[4 ,5] .就胶体晶体而言 ,用它作模板 ,几乎能制备包括无机、有机、金属、陶瓷的各种多孔材料 .自然界的蛋白石 (Ｏｐａｌｓ)是ＳｉＯ2 颗粒有序沉积物中 ,渗入水溶性硅酸盐 ,再在其中固化形成的 .按照自然形成蛋白石的模式 ,从胶体晶体复制 ,…     

Investigation of Pt–Ru nanoparticle catalysts for low temperature methanol electro-oxidation

Pt–Ru nanoparticle-based methanol electro-oxidation catalysts with high concentration of metallic phase on carbon black have been synthesised by a low-temperature colloidal preparation route. Amorphous Pt–Ru oxide nanoparticles were deposited on carbon and subsequently reduced in hydrogen stream at different temperatures to obtain crystalline phases with tailored particle size. The electro-catalytic activity for methanol oxidation was investigated in half-cell from 30 to 60 °C. The results were interpreted in terms of particle size, crystallographic structure, degree of alloying and carbon monoxide adsorption properties. The best performance was achieved for the catalyst with intermediate particle size in the investigated range. Furthermore, it is observed that the optimal properties for these catalysts depend on the operating temperature.     

Engineering DNA-mediated colloidal crystallization

DNA is a powerful and versatile tool for nanoscale self-assembly. Several researchers have assembled nanoparticles and colloids into a variety of structures using the sequence-specific binding properties of DNA. Until recently, however, all of the reported structures were disordered, even in systems where ordered colloidal crystals might be expected. We detail the experimental approach and surface preparation that we used to form the first DNA-mediated colloidal crystals, using 1 mum diameter polystyrene particles. Control experiments based on the depletion interaction clearly indicate that two standard methods for grafting biomolecules to colloidal particles (biotin/avidin and water-soluble carbodiimide) do not lead to ordered structures, even when blockers are employed that yield nominally stable, reversibly aggregating dispersions. In contrast, a swelling/deswelling-based method with poly(ethylene glycol) spacers resulted in particles that readily formed ordered crystals. The sequence specificity of the interaction is demonstrated by the crystal excluding particles bearing a noninteracting sequence. The temperature dependence of gelation and crystallization agree well with a simple thermodynamic model and a more detailed model of the effective colloidal pair interaction potential. We hypothesize that the surfaces yielded by the first two chemistries somehow hinder the particle-particle rolling required for annealing ordered structures, while at the same time not inducing a significant mean-force interaction that would alter the self-assembly phase diagram. Finally, we observe that particle crystallization kinetics become faster as the grafted-DNA density is increased, consistent with the particle-particle binding process being reaction, rather than diffusion limited.     

Effect of hydrophilic macro-RAFT agent in surfactant-free emulsion polymerization

Here we report, synthesis of different molecular weight poly (styrene sulfonate) based macro-RAFT agents and their use as shell material in surfactant-free emulsion polymerization of styrene. Concentration and molecular weight of hydrophilic macro-RAFT agent has an influence on colloidal stability, particle size distribution and self-assembly. Microscopic and zeta-potential studies of colloids reveal that, the macro-RAFT agents used with low molecular weight (M_n = 1200) are comparable more efficient than high molecular weight (M_n = 46,800 and 116,000) for imparting narrow particle size distribution with good colloidal stability.     

The feasibility of inert colloidal processing of silicon nanoparticles

Silicon nanoparticles have important applications, including nonvolatile floating-gate memory devices. To prevent device performance variations, particle size and oxide thicknesses need to be controlled with a high degree of precision. Additionally, producing well-ordered, two-dimensional arrays of nanoparticles may require the exploitation of self-assembly techniques and colloidal forces, which in turn requires that silicon nanoparticles first come into contact with liquids. Until recently, aerosol silicon nanoparticle collection into liquid was assumed to be an inert process. Once formed, the silicon nanoparticle colloid was assumed to be inert. In fact, silicon nanoparticles produced in the aerosol phase by dilute silane pyrolysis and size classified with a differential mobility analyzer undergo a size reduction upon collection in ethylene glycol, water, and ethanol. Unclassified polydisperse silicon aerosol nanoparticles with an average diameter of 11 nm become monodisperse when collected in a colloid and have a final particle diameter of 2-5 nm. Further evidence suggests that silicon nanoparticles collected in ethanol react with the ethanol to produce tetraalkylorthosilicate-like species. Collections of aerosol silicon nanoparticles in degassed water do not show measurable differences between the aerosol and colloidal size distributions. This reduced reactivity to the solvent indicates that the presence of dissolved oxygen in the solvent may be responsible for the reactivity between the silicon nanoparticles and the solvent.     

Kinetic stages of single-component colloidal crystallization

To harness the full potential of colloidal self-assembly, the dynamics of the transition between colloids in suspension to a colloidal crystalline film should be better understood. In this report, the structural changes during the self-assembly process in a vertical configuration for colloids in the size range 200-400 nm are monitored in situ, using the transmission spectrum of the colloidal assembly treated as an emergent photonic crystal. It is found that there are several sequential stages of colloidal ordering: in suspension, with a larger lattice parameter than the solid state, in a close-packed wet state with solvent in the interstices, and, finally, in a close-packed dry state with air in the interstices. Assuming that these stages lead continuously from one to another, we can interpret colloidal crystallization as being initiated by interparticle forces in suspension first, followed by capillary forces. This result has implications for identifying the optimum conditions to obtain high-quality nanostructures of submicrometer-sized colloidal particles.     

Pickering–Ramsden emulsions stabilized with chemically and morphologically anisotropic particles

Recent developments in nanotechnology have facilitated the use of surface-active colloidal particles with tailor-made anisotropic properties. These surface-active agents have introduced unprecedented emulsion systems that exhibit qualitatively different self-assembled/organized structures and material properties from those of emulsions with conventional surfactants or isotropic colloidal particles. The author highlights the recent experimental works that elucidate the fundamental roles of anisotropy in the self-assembly/organization in emulsions, while focusing predominantly on amphiphilicity and morphological anisotropy in a particle. The author also introduces recent works that harness these fundamental properties of anisotropy for realizing the characteristic emulsion state and its functionality, together with a work with large particles beyond colloidal scale.