Organophosphorus coupling agents bearing permanently charged functional groups (either cationic quaternary ammonium or anionic sulfonates) were synthesized and used for the modification of zirconia nanoparticles with a diameter <10 nm. Surface functionalization was confirmed by FTIR and solid-state NMR spectroscopy. Surface coverages up to 2.3−2.4 molecules/nm 2 were achieved for modification with these charged coupling agents. The pH-dependent charge measurements of homogeneously modified particles showed stable surface charges over a wide range of pH for both ammonium-and sulfonate-functionalized particles. Surface charge measurements of particles cofunctionalized with charged coupling molecules and uncharged methyl phosphonic acid revealed a decreasing charge density with increasing amount of uncharged coupling agent. Thus, an adjustment of charges by co-functionalization was obtained on the particle surface. The thus-formed surface-charged colloids were used in a second step for electrostatic-driven aggregation phenomena necessary for layer-by-layer processes. Sulfonate-modified negatively charged SiO 2 submicrometer particles of 506 nm in diameter were decorated with ammonium-modified ZrO 2 nanoparticles. In addition, a layer-by-layer deposition of alternating charge-modified TiO 2 nanoparticles was proven by optical spectroscopy. Due to the broad applicability of organophosphorus coupling agents for surface modification, particularly for transition-metal oxides, the shown route represents a general method for the creation of almost pH-independent charges on the surface of nanoparticles.
Carbon aerogels find application in many fields. In most of the applications, they are used as powders and thus need to be pulverized. However, the pulverization could induce various changes in the microstructure of carbon aerogels. The extent of changes depends not only on the dominant forces of used technique, but also on the mechanical and structural properties of initial monolithic samples. In the present work, we discuss the influence of grinding, milling in shaker cryo-mill, and planetary ball mill on stiff, ductile and flexible carbon aerogels. Scanning electron microscopy and transmission electron microscopy images, gas sorption techniques, wide-angle X-ray scattering, and Raman spectroscopy show a strong dependency of the introduced energy amount while pulverization on the structure modification. Results show that stiff carbon aerogels do not undergo noticeable changes. In contrast, ductile carbon aerogels are very sensitive to friction forces. Soft and flexible carbon aerogels undergo drastic changes in the microstructure.
Organic aerogels in the form of powder, microgranules and microsized particles receive considerable attention due to their easy fabrication, low process time and costs compared to their monolithic form. Here, we developed resorcinol-formaldehyde (RF) aerogel microparticles by using an emulsion-gelation method. The main objective of this study is to investigate the influence of curing time, stirring rate, RF sol:oil ratio and initial pH of the sol in order to control the size and properties of the microparticles produced. The emulsion-gelation of RF sol prepared with sodium carbonate catalyst in an oil phase at 60 °C was explored. RF microparticles were washed with ethanol to remove the oil phase followed by supercritical and ambient pressure drying. The properties of the dried RF microparticles were analyzed using FT-IR, N2 adsorption isotherm, gas pycnometry, wide angle X-ray scattering and scanning electron microscope. RF microparticles with high surface area up to 543 m2/g and large pore volume of 1.75 cm3/g with particle sizes ranging from 50–425 µm were obtained.
Anisotrope Partikel sind eine Materialklasse, die es erlaubt, multifunktionelle Eigenschaften in einen partikulär aufgebauten Festkörper zu induzieren. Dadurch können unterschiedliche Funktionen in ein und dasselbe Partikel eingebaut werden, beispielsweise unterschiedliche Polaritäten oder magnetische und optische Eigenschaften. Durch ihre außergewöhnliche Struktur, mit zwei unterschiedlichen Kompartimenten an der Oberfläche, erhielt diese Partikelart den Namen Janus‐Partikel. Für die Chemie besteht die Herausforderung in der Synthese solcher Partikel. Es muss dafür gesorgt werden, dass die Reaktionsräume auf der Längenskala der Partikel so differenziert werden, dass es zu einer Anisotropie von Wachstums‐ oder Funktionalisierungsprozessen kommt. Hierbei spielen insbesondere Reaktionen an Phasengrenzen eine wichtige Rolle. Mittlerweile ist eine Vielzahl an unterschiedlichen Janus‐Materialkombinationen bekannt und die ersten Systeme werden in technologischen Anwendungen verwendet.
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