Electron Microscopic Study on Aerosol-Assisted Synthesis of Aluminum Organophosphonates Using Flexible Colloidal PS-b-PEO Templates

A wide variety of synthetic approaches from homogeneous precursor solutions have so far been developed for precise structural design of materials in multiscale. In organic templating approaches for porous materials design, we have recently developed a new approach to fabricate colloidal polystyrene-block-poly(oxyethylene) (PS-b-PEO) templated large pores that can be controlled in thick films of aluminum organophosphonate (AOP). In this study, we extended this approach using colloidal PS-b-PEO aggregates to aerosol-assisted synthesis for the fabrication of spherical particles. Structural variations (morphology and porous structure) depended on the synthetic conditions, which were mainly investigated by using electron microscopies (SEM and TEM). In addition to the insight on the colloidal PS-b-PEO templating of spherical pores in AOP spheres, it was found that colloidal PS-b-PEO aggregates were flexible for further design of pore shape that was strongly affected by external morphology. In this context, we proposed this method as flexible colloidal PS-b-PEO templating to fabricate unusual macroporous structures during morphological control from precursor solutions containing colloidal PS-b-PEO aggregates. The insights will be promising for precise construction of unique devices using porous materials templated by colloidal organic aggregates. In addition, we found a useful water adsorption-desorption behavior over the macroporous AOP bulky powders when the macropores were connected through large pores, which is also significant for future development of AOP-based porous materials.     

Transmission X-ray microscopy reveals the clay aggregate discrete structure in aqueous environment

The utilization of new transmission X-ray microscopy (TXM) using the synchrotron photon source enable for the first time the study in three dimensions microsize clay particles in aggregates in their natural aqueous environment. This technique makes possible remarkable accurate images of nanosize mineral interparticle structure which forms a new nanocomposite. The Birdwood kaolinite/LDH aggregates observed in the TXM are much more compact than observed before in pure Birdwood kaolinite suspension and similar to aggregates formed after treatment by positively charged surfactant. Kaolinite/LDH aggregates in water reveal complex structure of larger kaolinite platelets connected together by gelled nanoparticles which are most probably LDH colloidal plates. Comparisons of the transmission electron microscope (TEM) and TXM techniques show similarities in particle morphology. The ability to study particles and aggregates in their natural aqueous environment and in 3-dimensions make this technique superior to the TEM technique.     

Synthesis of bifunctional core–shell particles with a porous zeolite core and a responsive polymeric shell

The aim of our work is the synthesis and characterization of colloidal core–shell particles with a zeolite core and an environmentally responsive shell. We have synthesized colloidal ZSM-5 zeolite and modified the surface with 3-(trimethoxysilyl)propyl methacrylate in order to introduce double bonds at the surface. The cross-linked polymeric shell was prepared by precipitation polymerization using the functionalized zeolite particles as seeds. We employed thermoresponsive poly(N-isopropylacrylamide) and pH-responsive poly(vinylpyridine) as the polymeric shell, respectively. The temperature- and pH-depending swelling and deswelling of the core–shell particles were characterized with dynamic light scattering techniques. Transmission electron microscopy pictures show the morphology of the synthesized particles. It is proposed that these types of bifunctional core–shell particles could be of use for controlled uptake and release applications and separation of molecules.     

ESI-TEM imaging of surfactants and ions sorbed in Stöber silica nanoparticles

The sorption of surfactants and NaCl in silica nanosized particles creates unexpected spatial distributions of solutes that were evidenced by electron spectroscopy imaging in the transmission electron microscope (ESI/TEM). The spectral images show that simple ions (Na(+), Cl(-), Br(-)) are actually absorbed within the particles irrespective of their charges, while surfactant chains are adsorbed at the particle surfaces. The expected effect of the surfactants on particle aggregation is also observed in the micrographs. In the case of salt, close-packed silica particle arrays are formed at low ionic strength, but only coarse aggregates form at higher salt concentrations. The particles absorb both Na(+) and Cl(-) ions in similar amounts, from 0.5 mol L(-)(1) NaCl, but Na(+) ions are depleted from the particles' immediate outer vicinity, where Cl(-) ions are in turn accumulated. These results confirm that St?ber silica nanoparticles are highly porous and reveal their potential usefulness as carriers of small molecules and ions, due to the small particle size, exceptional colloidal stability, and this newly found sorption behavior.     

Template-assisted self-assembly: a practical route to complex aggregates of monodispersed colloids with well-defined sizes, shapes, and structures

This paper describes a strategy that combines physical templating and capillary forces to assemble monodispersed spherical colloids into uniform aggregates with well-controlled sizes, shapes, and structures. When an aqueous dispersion of colloidal particles was allowed to dewet from a solid surface that had been patterned with appropriate relief structures, the particles were trapped by the recessed regions and assembled into aggregates whose structures were determined by the geometric confinement provided by the templates. We have demonstrated the capability and feasibility of this approach by assembling polystyrene beads and silica colloids (> or =150 nm in diameter) into complex aggregates that include polygonal or polyhedral clusters, linear or zigzag chains, and circular rings. We have also been able to generate hybrid aggregates in the shape of HF or H2O molecules that are composed of polymer beads having different diameters, polymer beads labeled with different organic dyes, and a combination of polymeric and inorganic beads. These colloidal aggregates can serve as a useful model system to investigate the hydrodynamic and optical scattering properties of colloidal particles having nonspherical morphologies. They should also find use as the building blocks to generate hierarchically self-assembled systems that may exhibit interesting properties highly valuable to areas ranging from photonics to condensed matter physics.     

Nanosized gismondine grown in colloidal precursor solutions

A colloidal molecular sieve with GIS-type structure was prepared from aged aluminosilicate precursor solutions containing tetramethylammonium (TMA) hydroxide under hydrothermal treatment at 100 degrees C. The nucleation and the development of the GIS zeolite structure were studied by dynamic light scattering, scanning electron microscopy, X-ray diffraction, Raman and infrared spectroscopies, and liquid-state NMR spectroscopy. It is shown that the aging at room temperature leads to the formation of subcolloidal particles that incorporate TMA cations and form larger aggregates. After an extended heating of 13 days, a complete transformation from amorphous precursor material to crystalline GIS-type colloidal particles is observed. The mean hydrodynamic radius of the crystalline GIS particles is in the range of 30-50 nm. The specific template-framework interactions influence the spectral features of the TMA cations incorporated in the zeolite structure, thus making possible the use of the corresponding Raman spectra and 13C NMR data for the examination of the crystallinity of GIS-type colloidal particles stabilized in water.     

Improving in situ liquid SEM imaging of particles

This work presents in situ imaging of synthesized boehmite (γ-AlOOH) particles ranging from 20 to 100 nm, suspended in liquid, in a vacuum compatible microfluidic sample holder using a scanning electron microscopy (SEM) under the high vacuum mode and highlights the advantage of in situ liquid imaging of colloids. Nanometer-sized boehmite particles in high-level radioactive wastes at the Hanford site are known to be difficult to dissolve and cause rheological problems for processing in the nuclear waste treatment plant. Therefore, it is important to characterize boehmite particles and understand how they form aggregates in the liquid state. Several technical advancements are made to optimize in situ liquid SEM chemical imaging resulting in the improved ability to obtain secondary electron (SE), backscattered electron (BSE) images, and energy dispersive X-ray spectroscopy (EDX) spectra. Moreover, our results show mixed particles could be studied and identified based on the particle shape and elemental composition using in situ SEM imaging and EDX. Thus, we provide a new and improved approach to observe the evolution of particle dispersion and stability in liquid under conditions similar to those in the waste tank.     

Conversion of colloidal aggregates into polymer networks on aging

After long-term aging, surfactant-mediated colloidal aggregates of sulfonated polyaniline (S-PANI) and poly(vinylidene fluoride) (PVF₂) converted into three-dimensional polymer networks, whereas colloidal crystals prepared from pure PVF₂ remained unaltered. A model, where the surfactant tails anchored from the colloidal particles interdigitate with time resulting in coalescence of the particles to form the network morphology, has been proposed. X-ray photoelectron spectroscopy (XPS) revealed higher relative abundances of carbon atoms on the surface of the polymer networks than those of the colloidal aggregates, which adequately supports the proposed model.     

Synthesis and real-time magnetic manipulation of a biaxial superparamagnetic colloid

Superparamagnetic colloidal plates were synthesized from tetrabutylammonium stabilized Ca(2)Nb(3)O(10) nanosheets and oleic acid-stabilized Fe(3)O(4) nanoparticles. Modification with 3-aminopropyltrimethoxysilane produces amine-terminated Ca(2)Nb(3)O(10) with an amine concentration of 0.43 +/- 0.06 groups per Ca(2)Nb(3)O(10) unit as follows from spectroscopic quantification with trinitrobenzenesulfonic acid as a dye. Treatment of the modified sheets in THF/ethanol with 5.3 nm oleic acid-stabilized magnetite nanoparticles yields pseudo-2D assemblies that consist of 2 nm thick nanosheets decorated on both sides with a dense collection (9.3 +/- 0.5 x 10(3) particles per square micrometer per side) of magnetite particles. In noncoordinating or weakly coordinating solvents, these composite particles further aggregate into stacked aggregates with a mean edge length of 1.6 +/- 0.7 microm and a thickness of 79 +/- 30 nm. The colloidal plates were characterized by elemental analysis, X-ray powder diffraction, and infrared and UV/vis spectroscopy. SQUID measurements show that films of the aligned particles are superparamagnetic at room temperature. The magnetic hysteresis that is observed at 5 K reveals that the plates have a magnetic anisotropy with the easy axis in the plane of the plates and the hard axis perpendicular to it. Calculations show that the magnetic anisotropy is a direct consequence of the two-dimensional distribution of the magnetic nanoparticles on the sheets. Optical microscopy reveals that when suspended in ethanol or THF, the colloidal plates can be rotated in real time with a variable external magnetic field (200 Oe). Magnetic alignment of the particles in suspensions also produces asymmetric light scattering patterns and magnetic birefringence. These effects and the observed magneto-orientational properties make the biaxial colloids interesting as components in displays and as magnetic actuators.     

聚乙烯吡咯烷酮稳定的钯纳米粒子催化加氢

Nanosized colloidal platinum was prepared by reduction of H2PtCl6 in methanol-water mixture by refluxing. The particle size and morphology were characterized by transmission electron microscopy and electron diffraction. The influence of polyvinylpyrrolidone (PVP) molecular mass (MM),PVP concentration,and reduction time on platinum particle size was investigated. Small (1-2 nm) Pt particles are formed in the case of PVP with MM=1.2×104. With increasing polymer MM and decreasing polymer concentration,large aggregates from small particles appear. High catalytic activity of the obtained colloidal platinum in hydrogenation of acetylene compounds is shown. The effect of Pt particle size on the catalytic activity was studied.     

Colloidal stability of bare and polymer-grafted silica nanoparticles in ionic liquids

The colloidal stability of bare and poly(methyl methacrylate) (PMMA)-grafted silica nanoparticles was studied in 1-alkyl-3-methylimidazolium ([C(n)mim])-based ionic liquids (ILs) with different anionic structures. The theoretical estimation of the colloidal interaction between monodispersed bare silica particles by using the Derjaguin-Landau-Verwey-Overbeek theory indicates that bare silica particles cannot be stabilized and they rapidly form aggregates in all the ILs used in this study. The instability of bare silica particles was experimentally confirmed by dynamic light scattering measurement and in situ transmission electron microscopy observations by utilizing the negligible vapor pressure of ILs. This evidence suggests that electrostatic stabilization is inefficient in ILs because of the high ionic atmosphere and the resulting surface-charge screening. The PMMA-grafted silica particles exhibited long-term colloidal stability in [C(4)mim][PF(6)] and [C(n)mim][NTf(2)], which are compatible with the grafted PMMA. On the other hand, the PMMA-grafted particles could not be stabilized in [C 4mim][BF 4] due to the poor solubility of the grafted PMMA in the IL. Effective steric stabilization is important for obtaining stable colloidal particles in ILs.     

Preparation and characterization of particles with small differences in polydispersity

Colloidal particles are widely used both in fundamental research and in materials science. One important parameter influencing the physical properties of colloidal materials is the particle size distribution (polydispersity) of the colloidal particles. Recent work on colloidal crystallization has demonstrated that even subtle changes in polydispersity can have significant effects. In this study we present centrifugation techniques for subtly manipulating the width and the shape of the particle size distribution, for polydispersities less than 10%. We use scanning electron microscopy as well as dynamic and static light scattering to characterize the particle size distributions. We compare the results and highlight the difficulties associated with the determination of accurate particle size distributions.     

Structure of polydispersed colloids characterised by light scattering and electron microscopy

The dynamics of growth and aggregation of colloidal silver iodide particles was followed by the static light scattering method. The particles were treated as spheres and they were stable in size in the defined time interval. This approach enabled the use of the Zimm plots in order to determine the radii of gyration and the radii of spherical particles. Stable AgI colloids, either positively or negatively charged, showed the usual Zimm diagrams, while the diagrams were untypical when the stability of the colloids decreased. The untypical Zimm diagrams showed 'curves' with envelopes and 'curves' with minima in the unstable domain and in the domain where the most rapid nucleation occurs, respectively. Satisfactory agreement of particle sizes within the limits of accuracy, determined using static--and dynamic light scattering data and of the values obtained from the electron microscopic images was shown. Fitting the theoretical and experimental data, P(theta) functions showed that the particle shapes approach the theoretical model for spheres and thin discs. The colloid stability of polydispersed aggregates was also explained using the second virial coefficient, its negative sign implying interaction of particles in the solution, its positive value indicating formation of new particles from the supernatant solution. In addition, the colloid stability can be characterised by the mass fractal dimension. For positive stable colloids, Dm = 2.70 +/- 0.26, it can be related to the reaction controlled processes, whereas for negative stable colloids, Dm = 1.97 +/- 0.19, it was attributed to the diffusion controlled processes.     

Obtaining of monodisperse particles through soap-free and seeded polymerization, respectively, through polymerization in the presence of C60

The present study reports on methods of synthesis of self-assembling monodisperse colloidal particles, obtained for the system styrene (St)–hydroxypropyl methacrylate, through emulsion polymerization, using no surfactant. The syntheses performed have led to the conclusion that the emulsion copolymerization in the presence of fullerene is responsible both for a significant decrease of the particles size as well as for a dimensional monodispersity of the system; the latter has been achieved also through seeded polymerization. The morphology and the size distribution of particles have been explored using scanning electron microscope and dynamic light scattering.     

Nano-Templates from Thermoresponsive Poly(ethoxytriethyleneglycol acrylate) for Polymeric Nano-Capsules

Temperature responsive poly(ethoxytriethyleneglycol acrylate) (PETEGA) of Mn = 8000 and M_w/M_n = 2.30 was synthesized by ATRP. Dilute aqueous solutions of PETEGA exhibit lower critical solution temperature (LCST) at around 34 °C. We found that PETEGA can form nano-sized uniform colloidal aggregates (50-200 nm) above LCST either with or without an additional surfactant. Therefore PETEGA nano-aggregates were used as templates for the seeded free radical copolymerization of acrylamides or methacrylates together with a cross-linker to form acrylamide or methacrylate based core-shell particles. The formation of the PETEGA templates was investigated by dynamic light scattering (DLS) in order to find optimal conditions for obtaining narrow dispersed aggregates of desired sub-micron dimensions. Core-shell particles were characterized by DLS and scanning electron microscopy.     

Redispergation of TiO2 particles in aqueous solutions

The colloidal stability of TiO2 dispersions in aqueous solutions was studied. Aqueous solutions of ATLAS G-3300 (1.57 x 10(-3) mol/l), TRITON X-100 (5 x 10(-5) mol/l), and PMAA (4 x 10(-6) and 5.81 x 10(-3) mol/l) have been used as medium for redispergation of TiO2 particles. Stability of dispersions was investigated at different pH values by two different methods. By using analytical centrifuge the sedimentation velocity of TiO2 particles was directly measured and by means of light scattering the particle size of dispersed particles has been monitored. Combination of these two methods allowed determination of the aggregation degree of TiO2 particles as well as structure of the aggregates formed in aqueous phase. It has been found that redispergation process does not provide complete separation of virgin TiO2 particles. Even in the case of stable dispersions some aggregates were found, which consisted of 2-4 virgin TiO2 particles. With increasing colloidal stability of dispersions aggregates appear to be spherically shaped. In the system where TRITON X-100 was used, formation of secondary aggregates by fusion of primary ones was observed.     

Spontaneous formation of micrometer-size inorganic peapods

We show that polyoxometalate (ammonium phosphomolybdate) Keggin in aqueous dispersions upon sonication spontaneously transforms into micrometer-sized, peapod-shaped structures. The formation of these peapods is preceded by the generation of spherical aggregates. The particles have been characterized experimentally by time-resolved dynamic light scattering (DLS), transmission electron microscopy (TEM), and scanning TEM with a high-angle annular dark field detector (STEM-HAADF) for energy-dispersive X-ray (STEM/EDX) elemental analyses. A pathway for the phenomenon is proposed.     

Nanodisperse systems as transient state upon the formation of crystalline organometalsiloxanes

Properties of colloidal solutions formed in the course of hydrolytic condensation of phenyltrialkoxysilanes are studied upon the synthesis of organosiloxanolates of alkali metals and cage-like bimetallic organometalsiloxanes containing alkali and transition (Ni, Cu) or rare-earth (Eu) metals. Sizes and shapes of particles are determined by the dynamic and static light scattering methods. The aggregation stability of colloidal solutions is studied as a function of solvent nature and concentration of phenyltrialkoxysilane. Data obtained make it possible to suggest that disclosed aggregates are the nuclei of crystalline phase. Conditions of the existence of stable colloidal aggregates of sodium phenylsiloxanolate and Ni/Na-phenylsiloxane are determined. It is shown that, upon the dissolution of crystalline Ni/Na-phenylsiloxane in butanol, particles whose sizes are comparable with molecules of organometalsiloxanes are formed in the initial solution.     

木质素基偶氮聚合物胶体球的制备

利用造纸废液中的碱木素(AL)合成了木质素基偶氮聚合物(AL-azo-COOEt), 并研究其自组装胶体化过程. 木质素偶氮聚合物的成功合成通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱和元素分析等表征方法得到证实. 激光光散射(LLS)监测了AL-azo-COOEt的胶体化过程, 自组装形成的胶体球利用透射电镜(TEM)、扫描电镜(SEM)、X射线光电子能谱仪(XPS)和元素分析等进行表征. 结果表明,木质素偶氮聚合物通过疏水聚集作用可以形成规整的实心胶体球, 且为内部较疏水外部较亲水性质的结构. 木质素偶氮聚合物胶体球可以包载疏水性药物阿霉素(DOX), 且其缓释性能可以通过缓冲溶液的pH值来调控.     

Evaporation‐Driven Self‐Assembly of Colloidal Silica Dispersion: New Insights on Janus Particles

The evaporation driven self‐assembly of novel colloidal silica Janus particles was evaluated by scanning electron microscopy in comparison to unfunctionalized silica particles. The cyclodextrin‐ and azobenzene‐modified compound was obtained utilizing Pickering emulsion approach, in which the particles were immobilized on solidified wax droplets and subsequently functionalized. Silica particles were modified with 3‐aminopropyl trimethoxysilane and afterward reacted with tosyl‐β‐CD or phenylazo(benzoic acid), respectively. Mesoscopic structures of the colloidal dispersions, as dried films from aqueous solution, have been investigated by scanning electron microscopy and dynamic light scattering. Interestingly, it has been observed that the Janus particles show a significantly different evaporation‐induced assembly than the unmodified particles.