Colloidal Deposition Research Articles

Robust continuous synthesis and in situ deposition of catalytically active nanoparticles on colloidal support materials in a triphasic flow millireactor

• A triphasic flow millireactor for nanoparticle synthesis and deposition is designed. • Tunability of nanoparticle loading on the support is demonstrated. • A versatile method shown for various support materials – TiO 2 , Al 2 O 3 and CeO 2 . • Mono-/bi-/tri- metallics nanoparticles are deposited on colloidal support material. Ultra-small noble metal nanoparticles, such as palladium, platinum and rhodium, are invaluable catalysts for the synthesis of a plethora of materials, ranging from pharmaceutical drugs to polymers and fertilizers due to their high catalytic activities and large surface area-to-volume ratios. In practice, these particles are typically deposited on larger-sized support materials to stabilize them against agglomeration, whilst maintaining catalytic activity. We choose colloidal deposition as the process to synthesize supported nanoparticles, as it enables the deposition of nanoparticles with complex compositions and shapes on the support material, since the physical properties of the colloid nanoparticles are not affected by the deposition process. In this paper, we demonstrate a robust triphasic flow millireactor for catalytic nanoparticle synthesis and their facile in situ deposition onto colloidal support materials with tunable metal loading from 5% to 23% and a high degree of control over the spatial distribution on the support material. We highlight the consistency and quality of the supported nanoparticles produced by the flow synthesis compared to their batch-synthesized counterparts. We also demonstrate the versatility of our method for different nanoparticles types, including bi-/tri-metallics (Pd 5 Pt 5 , Rh 5 Pt 5 , Ru 5 Pt 5 and Rh 3 Pd 4 Pt 5 ) and three different support materials - titania, alumina and ceria.

Enzymatic hydrolysis improves the stability of UHT treated faba bean protein emulsions

As an alternative to bovine milk, plant-based milks are gaining popularity in the global food market. However, industry faces various technological hurdles such as colloidal instability and sedimentation of these plant-based milk alternatives. Colloidal stability of UHT legume-based milk alternatives made from native and partially hydrolysed faba bean protein concentrate (FBPC) was investigated. FBPC was hydrolysed with alcalase for 5−90 min. Hydrolysates were assessed for physicochemical properties viz., degree of hydrolysis (DH), protein solubility, ζ-potential, and surface hydrophobicity. Extended enzymatic hydrolysis resulted in increased DH, protein solubility, higher electronegativity, and reduced surface hydrophobicity. Subsequently, oil-in-water emulsions (protein 5%) were prepared using either native FBPC or hydrolysates (DH 0–35%), 1% sunflower oil and 0.2% sunflower lecithin. These emulsions were homogenised and UHT treated, and then assessed for physicochemical properties. The findings revealed that emulsions stabilised by FBPC hydrolysates viz., 9 and 16% DH had better colloidal stability than native FBPC and other hydrolysates viz., 0–2, 30 and 35% DH, as indicated by droplet size, polydispersity index, flocculation index, coalescence index, surface charge and surface hydrophobicity. Overall, study showed that partial enzymatic hydrolysis of legume proteins may promote the colloidal stability of plant-based dairy alternative drinks.

Impact of heavy metal cations on deposition and release of clay colloids in saturated porous media

AbstractWhile the facilitated transport of heavy metals by colloids such as clay particles has been widely recognized, the influence of heavy metals on transport of the colloids has received much less attention. This study conducted saturated column experiments to systematically examine influence of multivalent heavy metal cations on transport of natural clay colloids and fullerene nC60 nanoparticles in glass bead porous media. Results showed that the presence of Cd2+ in the solution can cause more deposition of clay colloids in glass beads compared to Ca2+ at a given ionic strength (IS), and the subsequent release by IS reduction was less, demonstrating that the presence of Cd2+ increased the irreversibility of attachment. When the glass beads were initially adsorbed with Ca2+ and Cd2+, the release of clay colloids was significantly reduced due to strong cation bridge between the clay colloids and collector surfaces via the heavy metal cations. The release of clay colloids was significantly increased upon reduction of solution IS if the Na+ was used to exchange for the Ca2+ or Cd2+ before the IS reduction. Additional experiments showed that the nC60 nanoparticles that were deposited in the presence of Fe3+ and Cu2+ cannot be released by reduction of solution IS. However, the nanoparticle release occurred when the Ca2+ was used to exchange for the Fe3+ and Cu2+. Our work was the first to reveal the influence of heavy metal cations on the irreversibility of colloid attachment, and the findings have important implication to fabrication of functional nanomaterials for stabilization of heavy metals in soil and development of mathematic models for accurate prediction of cotransport of heavy metals and colloids in subsurface environments.

Colloidal stabilities and deposition behaviors of chromium (hydr)oxides in the presence of dissolved organic matters: role of coprecipitation and adsorption

The coprecipitation or surface adsorption of dissolved organic matters determined the colloidal stabilities and deposition behaviors of Cr (hydr)oxides.

Reduced deposition of 110mAg colloids by improved oxidation operation process during shutdown of a PWR

Reduced deposition of 110mAg colloids by improved oxidation operation process during shutdown of a PWR

Self-association and gel formation during sedimentation of like-charged colloids.

Formation of superstructures from colloidal dispersion involves a continuous increase in particle concentration, resulting in increasingly more complicated interparticle interaction. At high particle concentration, the presence of the super-crowding effect, strong non-ideality in addition to significant light absorption and scattering makes particle analysis very difficult. Here we report quantitative molecular, microscopic and macroscopic experimental results on like-charged colloids with concentration up to 60 vol%, close to the densest possible packing of spheres. It is achieved by conducting sedimentation-diffusion-equilibrium analytical ultracentrifugation (SE-AUC) on a concentrated dispersion of colloidal silica nanoparticles in a refractive-index-matching solvent. Surprisingly, we observed the self-association and even colloidal gel formation of like-charged colloids at very high concentration. Further experiments indicate that the attraction force may be counter-ion mediated. These results represent an important step forward in understanding complicated interparticle interaction in extremely high concentration, which is vital for the controlled fabrication of colloidal superstructures.

Deep‐Red‐Emitting Colloidal Quantum Well Light‐Emitting Diodes Enabled through a Complex Design of Core/Crown/Double Shell Heterostructure

AbstractExtending the emission peak wavelength of quasi‐2D colloidal quantum wells has been an important quest to fully exploit the potential of these materials, which has not been possible due to the complications arising from the partial dissolution and recrystallization during growth to date. Here, the synthetic pathway of (CdSe/CdS)@(1‐4 CdS/CdZnS) (core/crown)@(colloidal atomic layer deposition shell/hot injection shell) hetero‐nanoplatelets (NPLs) using multiple techniques, which together enable highly efficient emission beyond 700 nm in the deep‐red region, is proposed and demonstrated. Given the challenges of using conventional hot injection procedure, a method that allows to obtain sufficiently thick and passivated NPLs as the seeds is developed. Consequently, through the final hot injection shell coating, thick NPLs with superior optical properties including a high photoluminescence quantum yield of 88% are achieved. These NPLs emitting at 701 nm exhibit a full‐width‐at‐half‐maximum of 26 nm, enabled by the successfully maintained quasi‐2D shape and minimum defects of the resulting heterostructure. The deep‐red light‐emitting diode (LED) device fabricated with these NPLs has shown to yield a high external quantum efficiency of 6.8% at 701 nm, which is on par with other types of LEDs in this spectral range.

Improvement of the electrokinetic fluxes by tall fescue: Alleviation of ion attenuation and maintainability of soil colloidal properties

In this study, we aimed to address the attenuation of electrokinetic fluxes that occur during plant (tall fescue)-based electrokinetic remediation of oil-contaminated soil. Following 60 days of treatment, the concentration of water-soluble cations and anions in the electrokinetics-assisted phytoremediation treatment (EK-P) were 20.03 mg/kg and 15.7 mg/kg higher than that in the electrokinetic (EK) treatment, respectively. At the electrode, plants were able to alleviate the ion aggregation effect caused by the electrokinetics, reduce the conversion of soluble ions to insoluble ones, and reduce the decay of water-soluble ions. In addition, the zeta potential of EK-P was 5.05 mV lower than that of EK. Plants maintained the stability of the soil colloid and reduced the movement of the peak of colloidal particle size from small to large particles, thereby reducing the amount of colloidal deposition. Finally, the EK-P current was 22.49% higher than that in EK while the electrokinetic effect was maintained. Meanwhile, electrokinetics increased plant biomass by 20.21%. Electrokinetics was found to create a synergy with the plants, an effect that eventually enhanced the rate of oil degradation.

Photocatalytic Activity of Nanocoatings Based on Mixed Oxide V-TiO2 Nanoparticles with Controlled Composition and Size

V-TiO2 photocatalyst with 0 ≤ V ≤ 20 mol% was prepared via the sol–gel method based on mixed oxide titanium–vanadium nanoparticles with size and composition control. The mixed oxide vanadium–titanium oxo-alkoxy nanonoparticles were generated in a chemical micromixing reactor, coated on glass beads via liquid colloid deposition method and underwent to an appropriate thermal treatment forming crystallized nanocoatings. X-ray diffraction, Raman, thermogravimetric and differential thermal analyses confirmed anatase crystalline structure at vanadium content ≤ 10 mol%, with the cell parameters identical to those of pure TiO2. At a higher vanadium content of ~20 mol%, the material segregation began and orthorhombic phase of V2O5 appeared. The crystallization onset temperature of V-TiO2 smoothly changed with an increase in vanadium content. The best photocatalytic performance towards methylene blue decomposition in aqueous solutions under UVA and visible light illuminations was observed in V-TiO2 nanocoatings with, respectively, 2 mol% and 10 mol% vanadium.

Fluid flow and colloid transport experiment in single-porosity sample; tracking of colloid transport behavior in a saturated micromodel

Release of colloids and their subsequent transport into the subsurface environments takes place during a wide range of applications such as industrial, energy storage, and agricultural activities. Therefore, processes contributing to transport, attachment, and re-mobilization of colloids in porous media are attracting attention. A fraction of the released colloids may cross the soil vadose zone to reach the saturated groundwater. In this study, we explored colloid transport in a micromodel with high repulsion energy barrier where colloid retention is assumed to be low. Three major shortcomings were improved: pore space domain size, imaging resolution, and speed of imaging. The flow path of 1357 colloids with a size of 4 µm were tracked and these enabled precise determination of individual colloid transport mechanism as well as the integrated behavior of the system.Our direct observations have shown that even under unfavorable attachment conditions (defined based on the DLVO theory) colloids deposition occurred which was mainly due to the local flow velocity fluctuations and grain surface heterogeneity. Using the information from collective trajectories, we have quantified the contribution of differently behaved colloids in the observed breakthrough curve which show an integrated, macroscopic, behavior of the system and is often the only available information when performing column or field scale experiments to explore colloid transport in porous media. Furthermore, we have shown that attachment and remobilization of colloids increased the dispersion coefficient, and consequently the dispersivity value of the media.

Biochar-based nanocomposite from waste tea leaf for toxic dye removal: From facile fabrication to functional fitness

The present study utilized discarded tea leaf waste to produce ‘Tea leaf biochar’ (TLB) as the functional matrix for the fabrication of hybrid nanocomposite (nAg-TC), with colloidal deposition of silver nanoparticles (nAg) via modified chemical co-precipitation, for treatment of dye-laden wastewater. The chemical composition, physicochemical properties, and morphology of nAg-TC, and active surface functional groups involved in adsorption were identified using BET, FESEM-EDX, FTIR, TGA, XPS, and XRD. The nAg-TC matrix was found to be heterogeneous, mesoporous, thermostable, with rich in active surface functional groups (-OH, =NH, =CH, CC, CO, CN, and CC), and nAg as a dopant material. The dye adsorption results indicated the maximum removal efficiency (RhB = 95.89%, CR = 94.10%) at 300 K for rhodamine B (RhB) and Congo red (CR) concentrations of 25 mg L−1 and 22.5 mg L−1, respectively. The present investigation agreed with Freundlich isotherm (R2CR:0.991; R2RhB:0.993) and pseudo-second order kinetic (R2CR:0.999; R2RhB:0.999) model, indicating overall adsorption of RhB and CR through spontaneous and exothermic chemisorption on the heterogeneous surface of nAg-TC. The mechanism of RhB and CR adsorption was complex where nAg-TC, possessing the synergistic effects of TLB and nAg, showed surface complexation, electrostatic attraction, and H-bonding, leading to chemisorption. Study showed excellent reusability of spent nAg-TC, and commendable treatment efficiency for dye-laden real industrial effluents. The study exhibits substantial techno-economic feasibility of adsorbent and translates the principles of circular economy into synthesis of value-added products through sustainable management of biowaste and bioresource.

Features of colloidal silica deposits dip coated onto porous alumina membranes from aqueous suspensions

The present work is directed towards understanding the development of coating morphologies and the accompanying hydrodynamics of suspension flows during dip coating on porous substrates. Colloidal silica particles are deposited from aqueous suspension onto nanoporous alumina membranes. The choice of colloidal silica as the model system is motivated by its popularity in fabrication of antireflection coatings, and as nanostructured material templates for electrochemical and catalytic applications. Nanoporous alumina as substrate is notable for its chemical and thermal stability, and its ability to form self-organized pore structures. The objective here is to characterize the dependence of coating morphologies on membrane pore size, wettability, dip coating speed, and size of colloidal particles in suspension. A coating regime map is formulated based on different morphologies obtained for coatings deposited under different operating parameter spaces. The map indicates existence of two perceptibly distinct regimes which emanate from particle-induced interfacial deformation of the meniscus: Scarcely populated particulate deposition regime and densely packed coating regime having significant amount of particle deposition. The experimental results are analysed and explained using numerical results from earlier mathematical models in literature which cater to modified Landau-Levich formulation for porous substrates, as well as the hydrodynamics of colloidal assembly on moving substrates.

Colloidal Deposits via Capillary Bridge Evaporation and Particle Sorting Thereof.

Evaporating droplets of colloidal suspensions leave behind particle deposits which could be effectively controlled via manipulating the surrounding conditions and particles and liquid properties. While previous studies extensively focused on sessile and pendant droplets, the present work investigates the evaporation dynamics of capillary bridges of colloidal suspensions formed between two parallel plates. We vary the wettability of the plates and the particle size and composition of the colloidal suspensions, keeping the same spacing between the plates. We employ side visualization, optical microscopy, fluorescence microscopy, and scanning electron microscopy and develop computational and theoretical models to collect the data. A computational model based on diffusion-limited evaporation is used to characterize the timescale of the evaporation of the capillary bridge. The model predictions are in good agreement with the present and prior experimental measurements. We discuss about the deposits of monodispersed particle suspension formed by the interplay of pinning of the contact line and evaporation dynamics. Multiple rings on the plates are observed due to the stick-slip motion of the contact line. The larger particles tend to form asymmetric deposits, with most particles concentrated on the bottom plates due to a considerably stronger gravitational pull than the hydrodynamic drag. This deposition is explained by estimating the competing forces on the particles during the evaporation. A regime map is proposed for classifying deposits on the particle size wettability plane. Lastly, we demonstrate size-based particle sorting of bidispersed colloidal suspensions in this framework. We describe two mechanisms: gravity-assisted and geometry-assisted sorting, which can be designed to sort particles efficiently. A regime map depicting the regions of influence of each mechanism is presented.

Quality over Quantity: How Different Dispersion Qualities of Minute Amounts of Nano-Additives Affect Material Properties in Powder Bed Fusion of Polyamide 12.

The great interest, within the fields of research and industry, in enhancing the range and functionality of polymer powders for laser powder bed fusion (LB-PBF-P) increases the need for material modifications. To exploit the full potential of the additivation method of feedstock powders with nanoparticles, the influence of nanoparticles on the LB-PBF process and the material behavior must be understood. In this study, the impact of the quantity and dispersion quality of carbon nanoparticles deposited on polyamide 12 particles is investigated using tensile and cubic specimens manufactured under the same process conditions. The nano-additives are added through dry coating and colloidal deposition. The specimens are analyzed by tensile testing, differential scanning calorimetry, polarized light and electron microscopy, X-ray diffraction, infrared spectroscopy, and micro-computed tomography. The results show that minute amounts (0.005 vol%) of highly dispersed carbon nanoparticles shift the mechanical properties to higher ductility at the expense of tensile strength. Despite changes in crystallinity due to nano-additives, the crystalline phases of polyamide 12 are retained. Layer bonding and part densities strongly depend on the quantity and dispersion quality of the nanoparticles. Nanoparticle loadings for CO2 laser-operated PBF show only minor changes in material properties, while the potential is greater at lower laser wavelengths.

Colloidal transport and deposition through dense vegetation

The effectiveness of submerged synthetic aquatic vegetation on removal of colloids from flowing water was investigated to explore retention of particulate nonpoint source pollutants in aquatic systems. In colloid transport experiments, the deposition rate coefficient of colloids in dense vegetation is often taken as spatially constant. This assumption was tested by experiments and modeling aimed at quantifying changes in colloid retention with travel distance in submerged synthetic aquatic vegetation. Experiments were performed in a 10-m long, 0.6-m wide flume with a 5-cm water depth under different fluid velocities, initial colloid concentrations, and solution pH values. A model accounting for advection, dispersion and first-order kinetic deposition described the experimental data. The colloid deposition rate coefficient showed a power-law decrease with travel distance, and reached a steady state value before the end of the flume. Measured changes in colloid properties with transport distance (ζ potential and size) could not explain the observed decrease. While gravity was shown to contribute to the decrease, its impact was too weak to explain the decreasing power law trend, suggesting that processes operating in granular media to produce similar outcomes may also apply to submerged vegetation.

Use of organomineral sewage sludge for recultivation of disturbed by mining and processing industry lands

The paper is devoted to the study of the use of organic-mineral waste from the pulp and paper industry for the land and dumps restoration disturbed by the mining and processing industry. The examination of the chemical, agrochemical and toxicological properties of the dumps of the Verninsky GOK were carried out. It showed their toxicity to the environment and the need for restoration. It is proposed to use soil moisture obtained from frozen colloidal sediments of sludge-lignin of the Baikal PPM OJSC (BPPM) to intensify the restoration succession. It reduces the toxic effect of dumps on higher plants and introduces the necessary nutrients. At the same time, the use of the obtained soil moistures will make it possible not only to restore lands disturbed by the mining and processing industry, but also to utilize the accumulated waste of JSC BPPM, which creates a huge socio-ecological threat for Lake Baikal and the entire Southern Baikal region.

Colloidal deposition of colored daytime radiative cooling films using nanoparticle-based inks

In this study, we fabricated easily applicable and processible colored passive daytime radiative cooling (PDRC) films using a solution process with colloidal nanoparticle-based inks. White PDRC films were prepared using hollow silica nanoparticle (H–SiO2)-based colloidal inks and polymeric binders and spray coating. The films have an average reflectivity of 97.2% and emissivity of 94.3% and their temperature is 6.12 °C lower than the ambient temperature during the daytime at outdoor measurement. We also fabricated colored PDRC films by depositing Cu-based quantum dots (QDs) on white PDRC films. The Cu-based QDs partially absorb light in the visible spectrum, allowing yellow, red, and brown colors, that are highly efficient in preventing heat generation. The absorbed energy is converted into another wavelength and emitted as photons based on the photoluminescence effect. Based on the wavelength conversion, the yellow, red, and brown PDRC films can re-emit powers of 14.06, 28.36, and 43.92 W/m2, respectively, resulting in the prevention of heating. The results of outdoor measurements confirm that the temperature of the yellow and red PDRC films decreases by 3.25 and 0.51 °C, respectively, compared with the ambient temperature. Furthermore, we numerically and experimentally determined the daytime cooling performance of two brown PDRC films with different quantum efficiencies. Our results confirm that these easily processable colored PDRC films are more efficient daytime cooling than commercial paint color films on various substrates.

A multiscale quasilinear system for colloids deposition in porous media: Weak solvability and numerical simulation of a near-clogging scenario

We study the weak solvability of a macroscopic, quasilinear reaction–diffusion system posed in a 2D porous medium which undergoes microstructural problems. The solid matrix of this porous medium is assumed to be made out of circles of not-necessarily uniform radius. The growth or shrinkage of these circles, which are governed by an ODE, has direct feedback to the macroscopic diffusivity via an additional elliptic cell problem.The reaction–diffusion system describes the macroscopic diffusion, aggregation, and deposition of populations of colloidal particles of various sizes inside a porous media made of prescribed arrangement of balls. The mathematical analysis of this two-scale problem relies on a suitable application of Schauder’s fixed point theorem which also provides a convergent algorithm for an iteration method to compute finite difference approximations of smooth solutions to our multiscale model. Numerical simulations illustrate the behavior of the local concentration of the colloidal populations close to clogging situations.

Erratum: Fabrication of Zero Mode Waveguides for High Concentration Single Molecule Microscopy.

An erratum was issued for:Fabrication of Zero Mode Waveguides for High Concentration Single Molecule Microscopy. A figure was updated. Figure 3 was updated from: Figure 3: Representative results from evaporative deposition of colloids. (A) Example of optimal colloid deposition. (B) Example of an acceptable colloid deposition in which conditions were more humid (80% RH) than ideal. Holes in the crystal monolayer are apparent. (C) Example of an acceptable colloid deposition in which conditions were drier (65% RH) than optimal. The monolayer regions are slightly translucent while multilayered areas are white and opaque (perimeter and streaks inward). (D) A colloidal crystal illuminated with white light to highlight the rainbow diffraction from the crystals. (E) AFM image (tapping probe AFM in air) of a monolayer of hexagonally packed polystyrene beads from a successful colloid deposition (scale bar = 10 µm). (F) Expanded AFM image of packed beads (scale bar = 2 µm). Please click here to view a larger version of this figure. to: Figure 3: Representative results from evaporative deposition of colloids. (A) Example of optimal colloid deposition. (B) Example of an acceptable colloid deposition in which conditions were more humid (80% RH) than ideal. Holes in the crystal monolayer are apparent. (C) Example of an acceptable colloid deposition in which conditions were drier (65% RH) than optimal. The monolayer regions are slightly translucent while multilayered areas are white and opaque (perimeter and streaks inward). (D) A colloidal crystal illuminated with white light to highlight the rainbow diffraction from the crystals. (E) AFM image (tapping probe AFM in air) of a monolayer of hexagonally packed polystyrene beads from a successful colloid deposition (scale bar = 10 µm). (F) Expanded AFM image of packed beads (scale bar = 2 µm). Please click here to view a larger version of this figure.

Mechanisms of bentonite colloid aggregation, retention, and release in saturated porous media: Role of counter ions and humic acid

In the subsurface environment, colloids play an important role in pollutant transport by acting as the carriers. Understanding colloid release, transport, and deposition in porous media is a prerequisite for evaluating the potential role of colloids in subsurface contaminant transport. In this work, the aggregation, retention, and release of bentonite colloid in saturated porous sand media were investigated by kinetic aggregation and column experiments, the correlation and mechanism of these processes were revealed by combining colloid filtration theory, interaction energy calculation and density functional theory. The results showed that the retention and release of colloids were closely related to the dispersion stability and filtration effect. Multivalent cations with higher mineral affinity reduced the colloid stability, and the dispersion stability and mobility of the colloid were greatly improved by humic acid due to the enhancement of electrostatic repulsion and steric hindrance effects. The primary minimum interaction was found to contribute more to irreversible colloid retention in a Ca2+ system, while the secondary energy minimum was found to be responsible for colloid release with the occurrence of transient solution chemistry. The deposited colloid aggregates could be redistributed and released when the solution chemistry became favorable towards dispersion. These findings provide essential insight into the environmental colloid fate as well as a vital reference for the risk of colloid-driven transport of contaminants in the subsurface aquifer environment.