Numerous studies have demonstrated the bottom-up assembly of complex structures such as colloidal crystals, close-packed aggregates, and even rings and tetramers. In this paper we produce a simple localized and nanoscale charge distribution on the surfaces of individual colloidal microspheres using our technique of "particle lithography". In this technique parts of the microspheres are masked off, while polyelectrolytes (or other molecules) cover the remaining portions of the microspheres. The effectiveness of this process is demonstrated by the accurate and reproducible production of colloidal heterodoublets composed of oppositely charged microspheres. These "colloidal molecules" have the potential for significantly higher information content than previous attempts in the literature. The particle lithography technique is advantageous because it is not limited by the resolution of photolithography or by functionalizing chemistries, and the technique opens the door for complex site-specific functionalization of particles.
Individual colloidal particles are locally functionalized with nanoscale control. Here we use the particle lithography technique to mask one region of a silica or polystyrene particle (size 3.0 mum down to 170 nm), while the remaining 95% or more of the particle is coated with various sized nanocolloids. The images and data show precise and predictable control over the size of the region, with fine-tuned patch size control obtainable by changing the ionic strength of the solution. The coating on the particles remains stable even when subjected to sonication for 5 min. Both single regions and multilayer annuluses are readily formed. Particle lithography provides a general, reliable, stable, controllable, and scalable method for placing site-specific functionalizations on individual particles, opening the way to more complex particle patterning and the bottom-up assembly of more complex structures.
It is well-known that high ionic strength promotes colloid aggregation. Here we show that, by controlling this aggregation process, we can produce high yields of homodoublet and heterodoublet polymer colloids. The aggregation process is started by increasing the ionic strength to roughly 250 mM KCl. After approximately the rapid flocculation time, we quench the "reaction" by mixing in a large quantity of deionized water, which dilutes the ionic strength and prevents further aggregation. At this point, the suspension consists primarily of singlet and doublet particles. Through heating above the glass transition temperature of the polymers, the doublets are fused together and remain intact even after sonication. It is also shown that heterodoublets can include a silica particle together with a polymer colloid. The salting out-quenching-fusing technique is a rapid, easy-to-perform, repeatable process for fabricating colloidal doublets from polymers and other materials.
Colloidal particles with heterogeneous surfaces offer rich possibilities for controlled self-assembly. We have developed a method for preparing micrometer-sized polystyrene spheres with circular flat spots of controlled radius and location. The flats are created by settling the particles onto a flat glass substrate and then raising the temperature above the glass-transition temperature of the polymer for a controlled time (t). The polymer particle spreads on the glass such that the radius of the flat grows with time. We present a scaling theory for the hydrodynamics of the flattening process, finding that the radius of the flat grows as t(1/3). The model is in good agreement with our experimental observations of the flat radius versus spreading time as well as with previous studies in the literature for sintering polymer spheres.
For bottom-up particle fabrication, separation of complex particle assemblies from their precursor colloidal building blocks is critical to producing useable quantities of materials. The separations are often done using a density gradient sedimentation due to its simplicity and scalability. When loading density gradients at volume fractions greater than 0.001, however, an inherent convective instability arises. By translating the Rayleigh-Benard instability from the heat-transfer literature into an analogous mass-transfer problem, the variables affecting the critical stability limit were effectively catalogued and examined. Experiments using submicrometer particles loaded onto sucrose and Ficoll density gradients matched theoretical trends and led to a series of useful heuristics for prolonging density gradient stability. Higher particle loading heights, lower volume fractions, and smaller gradient material diffusion coefficients were found to improve stability. Centrifugation was useful at short times, as particles were removed from top of the gradient where the stable density profile degrades to unstable, and the resulting density inversion arises as the sucrose diffuses upward.
Instabilities often arise in the sedimentation of colloidal particles, even when using the density gradient technique. These instabilities occur at volume fractions as low as 10−3 or 10−4, causing mixing of particles throughout the suspension, rather than the smooth sedimentation of particles. Here, we show that the mixing is due to a classical Rayleigh−Bénard instability. The sedimentation process is modeled in an approximate manner, and experiments are done to test whether the approximate model gives maximum stable volume fractions in the correct range. Sedimentation is a well-studied problem, and yet, to our knowledge, this is the first time that the well-known instability has been described in terms of a Rayleigh−Bénard instability.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.