Colloidal Deposition Research Articles

Stains from Freeze-Dried Drops.

The evaporation of droplets of colloidal suspensions onto a surface is a common tool to achieve surface coatings and self-assembly. However, because of the spontaneous flow developing within an evaporating drop, the deposit is difficult to control, and an unwanted ring-like structure often forms, with particles aggregating along the drop edge. Here, by freezing the drops before sublimating them in dry air we propose a new approach that produces a different kind of stain where most particles are clustered in the center of the drops instead. We demonstrate that these deposits can be continuously tuned from wide but thin to concentrated and thick by varying the droplet’s aspect ratio. Unlike evaporated liquid drops, stains from freeze-dried drops do not depend on the drying conditions or substrate roughness and possess a porous and branched microstructure somewhat reminiscent of freeze-casted ceramics. With these stains being governed by the freezing process rather than the drying, this opens alternative ways to control colloidal deposits.

Recent Developments on Colloidal Deposits Obtained by Evaporation of Sessile Droplets on a Solid Surface

Understanding flow patterns and coupled transport phenomena during evaporation of droplets loaded with colloidal particles is central to design technical applications such as organizing proteins/DNA on a solid surface. We review recent reports on evaporating sessile droplets of colloidal suspensions on a solid surface. Starting from the classical mechanism of formation of a ring-like deposit, we discuss the influence of several problem parameters. Notably, thermal or solutal Marangoni effect, particle size, particle concentration, particle shape, substrate wettability, pH of the suspension etc have been found important in controlling the deposition pattern. The deposit pattern complexity and shape have been attributed to the underlying coupled transport phenomena during the evaporation. We discuss important regimes maps reported for different types of deposit, which allow us to classify the deposits and coupled physics. We also present studies that have demonstrated particles sorting in an evaporating bi-dispersed colloidal suspensions on a solid surface. Finally, some remarks for the future research opportunities in this arena are presented.

Aluminum alloy corrosion in boron‐containing alkaline solutions

Corrosion of aluminum alloy 1100 exposed to the boron‐containing alkaline solutions was studied. Test solutions were in the pH 7.5–8.2 range at 25, 55, and 85 °C. Both post‐tested aluminum alloy and alkaline solution were analyzed to characterize corrosion. The results indicate that the oxide layer at 25 and 55 °C was gibbsite Al(OH)3, and at 85 °C was boehmite AlOOH. Colloid deposits were found on the sample surface at 85 °C because of the phase transition of dissolved corrosion products with aging. The physics‐based aluminum release model for each test condition was developed to simulate the progression of aluminum concentration in the solution. Based on the model, the mass transfer coefficient of each test condition can be obtained.

Highly Stable, Near-Unity Efficiency Atomically Flat Semiconductor Nanocrystals of CdSe/ZnS Hetero-Nanoplatelets Enabled by ZnS-Shell Hot-Injection Growth.

Colloidal semiconductor nanoplatelets (NPLs) offer important benefits in nanocrystal optoelectronics with their unique excitonic properties. For NPLs, colloidal atomic layer deposition (c-ALD) provides the ability to produce their core/shell heterostructures. However, as c-ALD takes place at room temperature, this technique allows for only limited stability and low quantum yield. Here, highly stable, near-unity efficiency CdSe/ZnS NPLs are shown using hot-injection (HI) shell growth performed at 573 K, enabling routinely reproducible quantum yields up to 98%. These CdSe/ZnS HI-shell hetero-NPLs fully recover their initial photoluminescence (PL) intensity in solution after a heating cycle from 300 to 525 K under inert gas atmosphere, and their solid films exhibit 100% recovery of their initial PL intensity after a heating cycle up to 400 K under ambient atmosphere, by far outperforming the control group of c-ALD shell-coated CdSe/ZnS NPLs, which can sustain only 20% of their PL. In optical gain measurements, these core/HI-shell NPLs exhibit ultralow gain thresholds reaching ≈7 µJ cm-2 . Despite being annealed at 500 K, these ZnS-HI-shell NPLs possess low gain thresholds as small as 25 µJ cm-2 . These findings indicate that the proposed 573 K HI-shell-grown CdSe/ZnS NPLs hold great promise for extraordinarily high performance in nanocrystal optoelectronics.

Analysis of profile and morphology of colloidal deposits obtained from evaporating sessile droplets

We experimentally investigate the profile and morphology of the ring-like deposits obtained after evaporation of a sessile water droplet containing polystyrene colloidal particles on a hydrophilic glass substrate. In particular, the coupled effect of particle size and concentration are studied. The deposits were qualitatively visualized under an optical microscope and profile of the ring was measured by an optical profilometer. The profile of the ring resembles a partial torus-like shape for all cases of particles size and concentration. The cracks on the surface of the ring were found to occur only at smaller particle size and larger concentration. We plot a regime map to classify three deposit types - discontinuous monolayer ring, continuous monolayer ring, and multiple layers ring - on particles concentration - particle size plane. Our data shows a possible existence of a critical concentration (particle size) for a given particle size (concentration) at which the monolayer ring forms. For the larger particle sizes, the immersion capillary forces between the particles dominate, aiding the formation of a monolayer ring of the particles. We measure the width and height of the ring and show that they scale with particle concentration by a power law for the multiple layers ring. This scaling corroborates with an existing continuum based theoretical model. We briefly discuss the effect of the interaction of growing deposit with shrinking free surface on the ring dimensions and profile. The present results aid understanding of the ring formation process and will be useful in guiding the design of self-assemblies of the colloidal particles formed by the evaporating droplets.

Harnessing complex fluid interfaces to control colloidal assembly and deposition

HypothesisCapillary interactions play an important role in directing colloidal assembly on fluid interfaces. Interface curvature is expected to influence not only individual particle migration on interfaces but also capillary forces between nearby particles. In drying droplets, we hypothesize that the assembly and deposition of particles bound to droplet surface are controlled by the interplay between capillary effects and evaporation-driven flow. ExperimentsUsing lattice Boltzmann–Brownian dynamics (LB–BD) simulations, we modeled large-scale assembly of nanoparticles on fluid interfaces that have complex geometries and investigate the subsequent deposition upon complete evaporation. A systematic study was performed for geometrically-controlled sessile droplets whose surfaces exhibit varying curvature fields. FindingsThe simulations show that the particle dynamics on nonuniformly curved interfaces are anisotropic and governed by particle-pair capillary interactions and curvature-induced capillary migration. A theoretical model was developed to predict the capillarity-induced assembly. Using the curved surface as a template, drying droplets with surface-bound particles deposit distinct patterns as a result of the competition between the capillary effects and evaporation-induced convection. These findings could provide new opportunities in the directed assembly and deposition of colloidal particles with potential applications in fabricating functional materials from nanoscale building blocks.

Electrostatically Directed Assembly of Nanostructured Composites for Enhanced Photocatalysis

AbstractIt is well established that the activity of photocatalysts can be improved by deposition of redox catalysts, which can effectively extract the photogenerated charge carriers, enhance the rate of interfacial reactions, and thus suppress undesired recombination processes. For optimum performance, a high degree of control over the loading, size, and surface catalytic properties of redox catalyst particles is desirable. Herein, a novel, highly controllable, and versatile method for preparation of TiO2 catalyst composites is reported. It starts with the generation of “naked” (ligand‐free) nanoparticles of CuOx or FeOx by pulsed laser ablation of metal oxide targets in water. In the next step, a nearly quantitative colloidal deposition of CuOx and FeOx nanoparticles onto anatase TiO2 substrate is achieved by adjusting the pH in order to establish electrostatic attraction between the colloids and the substrate. The resulting TiO2–CuOx and TiO2–FeOx assemblies with optimum catalyst amount (≈0.5 wt%) exhibit photocatalytic rates in degradation of 2,4‐dichlorophenoxyacetic acid enhanced by a factor of ≈1.5 as compared to pristine TiO2 under simulated solar irradiation. The electrostatically directed assembly of TiO2 with ligand‐free catalyst nanoparticles generated by pulsed laser ablation is thus demonstrated as a viable tool for preparation of composites with enhanced photocatalytic performance.

Highly Transparent, Flexible Conductors and Heaters Based on Metal Nanomesh Structures Manufactured Using an All-Water-Based Solution Process.

Metal mesh is a promising material for flexible transparent conducting electrodes due to its outstanding physical and electrical properties. The excellent control of the sheet resistance and transmittance provided by the metal mesh electrodes is a great advantage for microelectronic applications. Thus, over the past decade, many studies have been performed in order to realize high-performance metal mesh; however, the lack of cost-effective fabrication processes and the weak adhesion between the metal mesh and substrate have hindered its widespread adoption for flexible optoelectronic applications. In this study, a new approach for fabricating robust silver mesh without using hazardous organic solvents is achieved by combining colloidal deposition and silver enhancement steps. The adhesion of the metal mesh was greatly improved by introducing an intermediate adhesion layer. Various patterns relevant to optoelectronic applications were fabricated with a minimum feature size of 700 nm, resulting in high optical transmittance of 97.7% and also high conductivity (71.6 Ω sq-1) of the metal mesh. In addition, we demonstrated an effective transparent heater using the silver mesh with excellent exothermic behavior, which heated up to 245 °C with 7 V applied voltage.

Scalable synthesis of gyroid-inspired freestanding three-dimensional graphene architectures

Three-dimensional porous architectures of graphene are desirable for energy storage, catalysis, and sensing applications. Yet it has proven challenging to devise scalable methods capable of producing co-continuous architectures and well-defined, uniform pore and ligament sizes at length scales relevant to applications. This is further complicated by processing temperatures necessary for high quality graphene. Here, bicontinuous interfacially jammed emulsion gels (bijels) are formed and processed into sacrificial porous Ni scaffolds for chemical vapor deposition to produce freestanding three-dimensional turbostratic graphene (bi-3DG) monoliths with high specific surface area. Scanning electron microscopy (SEM) images show that the bi-3DG monoliths inherit the unique microstructural characteristics of their bijel parents. Processing of the Ni templates strongly influences the resultant bi-3DG structures, enabling the formation of stacked graphene flakes or fewer-layer continuous films. Despite the multilayer nature, Raman spectra exhibit no discernable defect peak and large relative intensity for the Raman 2D mode, which is a characteristic of turbostratic graphene. Moiré patterns, observed in scanning tunneling microscopy images, further confirm the presence of turbostratic graphene. Nanoindentation of macroscopic pillars reveals a Young's modulus of 30 MPa, one of the highest recorded for sp2 carbon in a porous structure. Overall, this work highlights the utility of a scalable self-assembly method towards porous high quality graphene constructs with tunable, uniform, and co-continuous microstructure.

Deposition of carbon coatings by PVD-methods on polyurethane

Abstract In this article are compared the physico-mechanical properties of the specimens surfaces with deposited carbon nanostructured coatings by using PVD methods (vacuum laser assisted deposition and the plasma ion-assisted deposition methods and finely dispersed and colloidal solutions deposition) on polyurethane substrate. Laser assisted deposition occurred using two laser systems: continuous wave and pulsed laser action. The surface properties of the base substrate and the carbon coatings which were deposited on the polyurethane by using different methods have been investigated. The studies of the microstructure, topology, coatings thickness, roughness and the contact wetting angle were carried out by using the scanning electron, atomic force and optical microscopies.

Discovering a selective semimetal element to increase hematite photoanode charge separation efficiency

A colloidal deposition process combined with the thermal spreading ability of Sb over hematite surface is used to obtain a mesoporous photoanode for water oxidation.

Large-scale colloidal films with robust structural colors

“Milk skin”-analogous ensembles enable fine control over colloid deposition processes, allowing their universal use for uniform nanomaterial patterning.

Permeate flux increase by colloidal fouling control in a vibration enhanced reverse osmosis membrane desalination system

Experiments and Computational Fluid Dynamics (CFD) simulations were performed to investigate the colloidal fouling control of a vibration enhanced reverse osmosis (VERO) membrane system for up to 12 h of operation time. A porous cake mass transfer model for the reverse osmosis (RO) colloidal fouling analysis was derived by combining the cake filtration model, cake enhanced osmotic pressure (CEOP) effect, the critical flux theory, and the solute convection-diffusion model. The process of colloidal particle deposition and fouling formation on the membrane surface were visualized using this model. The permeate flux variation and cake layer distribution along the membrane were depicted. Systematic studies including different initial permeate fluxes, Reynolds numbers, particle concentrations, and vibration frequencies were carried out to investigate the system performance under different operation conditions. The results suggest that colloidal fouling induced permeate flux decline could be improved by the high-frequency vibration in the VERO module. Both simulations and experiments demonstrated that, with a fixed vibration amplitude, membrane module with higher vibration frequencies will have less NaCl accumulation and higher permeate flux under the influence of colloidal fouling.

HgTe/CdTe and HgSe/CdX (X = S, Se, and Te) Core/Shell Mid-Infrared Quantum Dots

Mid-infrared core/shell quantum dots are synthesized starting with HgTe and HgSe cores which emit around 5 μm with interband and intraband transitions, respectively. HgTe/CdTe and HgSe/CdX (X = S, Se, and Te) are grown by colloidal atomic layer deposition at room temperature. HgSe/CdSe is also grown by hot-injection. For films of the core/shells, even a two-monolayer shell leads to a vastly improved stability against annealing, with no observable changes up to the alloying temperatures of ∼180 °C for HgTe/CdTe and ∼250 °C for HgSe/CdX. The improvement in the photoluminescence remains however small for all systems. In this study across interband and intraband emissions, the brightest emitter at 5 μm is the intraband transition of HgSe/CdSe with a quantum yield of ∼10–3.

Deposition Kinetics of Colloidal Manganese Dioxide onto Representative Surfaces in Aquatic Environments: The Role of Humic Acid and Biomacromolecules.

The initial deposition kinetics of colloidal MnO2 on three representative surfaces in aquatic systems (i.e., silica, magnetite, and alumina) in NaNO3 solution were investigated in the presence of model constituents, including humic acid (HA), a polysaccharide (alginate), and a protein (bovine serum albumin (BSA), using laboratory quartz crystal microbalance with dissipation monitoring equipment (QCM-D). The results indicated that the deposition behaviors of MnO2 colloids on three surfaces were in good agreement with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Critical deposition concentrations (CDC) were determined to be 15.5 mM NaNO3 and 9.0 mM NaNO3 when colloidal MnO2 was deposited onto silica and magnetite, respectively. Both HA and alginate could largely retard the deposition of MnO2 colloids onto three selected surfaces due to steric repulsion, and HA was more effective in decreasing the deposition rate relative to alginate. However, the presence of BSA can provide more attractive deposition site and thus lead to greater deposition behavior of MnO2 colloids onto surfaces. The dissipative properties of the deposited layer were also influenced by surface type, electrolyte concentration, and organic matter characteristics. Overall, these results provide insights into the deposition behavior of MnO2 colloids on environmental surfaces and have significant implications for predicting the transport potential of common MnO2 colloids in natural environments and engineered systems.

Sedimentation of self-propelled Janus colloids: polarization and pressure

We study experimentally—using Janus colloids—and theoretically—using Active Brownian Particles—the sedimentation of dilute active colloids. We first confirm the existence of an exponential density profile. We show experimentally the emergence of a polarized steady state outside the effective equilibrium regime, i.e. when the sedimentation speed vs is not much smaller than the propulsion speed v0. The experimental distribution of polarization is very well described by the theoretical prediction with no fitting parameter. We then discuss and compare three expressions which have been proposed to measure the pressure of sedimenting particles: the weight of particles above a given height, the flux of momentum and active impulse, and the force density measured by pressure gauges.

Combined Computational and Experimental Study of CdSeS/ZnS Nanoplatelets: Structural, Vibrational, and Electronic Aspects of Core-Shell Interface Formation.

In the past few years, core-shell nanoparticles have opened new perspectives for the optoelectronic applications of semiconductor quantum dots. In particular, it has become possible to localize electrons in either part of these heterostructures. Understanding and controlling this phenomenon require a thorough characterization of the interfaces. In this study, we prepared quasi-2D CdSeS/ZnS core-shell nanoplatelets (NPLs) by colloidal atomic layer deposition. This technique allows fine control over the quantum confinement, the surfaces, and the interfaces. The layer-by-layer formation of a the ZnS shell around the CdSeS core was monitored using UV-vis absorption, XRD, and Raman spectroscopy. The measured band gaps and structural distortions were compared with results obtained from density functional theory (DFT) calculations. Modeling has also shown that 34% of the photoexcited electrons are delocalized into the ZnS shell. The herein presented combined modeling and experimental characterization strategy is of general interest since it can be applied to a large choice of layered semiconductor heterostructures in optoelectronics. The present approach paves the way for the synthesis of nanocrystals with precisely engineered properties for light-emitting diodes and solar cells.

Photocatalytic Nanoparticulate ZrxTi1‐xO2 Coatings with Controlled Homogeneity of Elemental Composition

AbstractThe mixed oxide ZrxTi1‐xO2 nanoparticulate photocatalysts of different compositions (0≤x≤1) were prepared via sol‐gel method in a rapid micromixing reactor followed by chemical colloid deposition on borosilicate glass beads, drying and heat treatment at temperatures between 400 to 650 °C. The point‐like reaction conditions in the regime of low Damköhler numbers resulted in nucleation of size‐selected reactive zirconium‐titanium oxo‐alkoxy (ZTOA) nanoparticles from zirconium (IV) propoxide and titanium (IV) isopropoxide precursors, which enable strong covalent bonds with hydrophilic supports. The ZTOA nanoparticles with compositions 0≤x≤0.2 convert after a heat treatment to nanoporous monocrystals in distorted anatase phase. The photocatalytic activity of the prepared nanoparticulate coatings on gaseous ethylene decomposition attained maximum at x=0.043 after heat treatment at 500 °C, which was two times higher than that of pure anatase TiO2. A net correlation between the material photocatalytic activity and amplitude of the slow power decay of photoinduced charges was observed. A model is proposed explaining the power law decay by a thermal release of the localised charges from shallow surface Urbach states. The number density of these states is connected to the specific surface area of the photocatalyst.

Magnetic Nano-Sized Solid Acid Catalyst Bearing Sulfonic Acid Groups for Biodiesel Synthesis

Abstract In our approach for magnetic iron oxide nanoparticles surface modification, the fabrication of an inorganic shell, consisting of silica by the deposition of preformed colloids onto the nanoparticle surface and functionalization of these particles, was realized. The magnetic nanoparticles, non-coated and coated with silica layer by Stöber method, are functionalized with chlorosulfonic acid. The magnetic nanoparticles (MNPs), in size of 10-13 nm, could be used as acid catalyst in biodiesel production and show superparamagnetic character. The prepared nanoparticles were characterized by different methods including XRD, EDX, FT-IR and VSM. The catalytic activity of the coated and non-coated solid acids was examined in palmitic acid-methanol esterification as an industrial reaction for biodiesel synthesis. Although thin silica layer results in only a minor obstacle with respect to magnetism, it can accelerate the mass transportation due to its relatively porous structure and magnetic core may be more stable in the acidic reaction medium by means of covering process. Accordingly, coating strategy can be efficient way for allowing applications of MNPs in acid catalyzed esterification.

Catalytic Performance of Gold Supported on Mn, Fe and Ni Doped Ceria in the Preferential Oxidation of CO in H2-Rich Stream

Ceria supported metal catalysts often exhibit high activity in the preferential oxidation (PROX) of CO in H2-rich stream and doping the ceria support with other metals proves to be rather effective in further enhancing their catalytic performance. Therefore, in this work, a series of ceria materials doped with Mn, Fe and Ni (CeM, where M = Mn, Fe and Ni; M/Ce = 1/8) were synthesized by a modified hydrothermal method; with the doped ceria materials (CeM) as the support, various supported gold catalysts (Au/CeM) were prepared by the colloidal deposition method. The influence of metal dopant on the performance of these ceria materials supported with gold catalysts in CO PROX was then investigated in detail with the help of various characterization measures such as N2 sorption, XRD, TEM, Raman spectroscopy, H2-TPR, XPS and XAS. The results indicate that the incorporation of Mn, Fe and Ni metal ions into ceria can remarkably increase the amount of oxygen vacancies in the doped ceria support, which is beneficial for enhancing the reducibility of ceria, the metal-support interaction and the dispersion of gold species. Although the gold catalysts supported on various doped ceria are similar in the size and state of Au nanoparticles, the CO conversions for CO PROX over Au/CeMn, Au/CeFe and Au/CeNi catalysts are 65.6%, 93.0% and 48.2%, respectively, much higher than the value of 33.6% over the undoped Au/CeO2 catalyst at ambient temperature. For CO PROX over the Au/CeNi catalyst, the conversion of CO remains near 100% at 60–130 °C, with a PROX selectivity to CO2 of higher than 50%. The excellent performance of Au/CeNi catalyst can be ascribed to its large amount of oxygen vacancies and high reducibility on account of Ni incorporation. The insight shown in this work helps to clarify the doping effect of other metals on the physicochemical properties of ceria, which is then beneficial to building a structure-performance relation for ceria supported gold catalyst as well as developing a better catalyst for removing trace CO in the hydrogen stream and producing high purity hydrogen.