Binary Colloids Research Articles

Binary Self-Assembly of Nanocolloidal Arrays using Concurrent and Sequential Spin Coating Techniques.

This paper reports the binary colloid assembly of nanospheres using spin coating techniques. Polystyrene spheres with sizes of 900 and 100 nm were assembled on top of silicon substrates utilizing a spin coater. Two different spin coating processes, namely concurrent and sequential coatings, were employed. For the concurrent spin coating, 900 and 100 nm colloidal nanospheres of latex were first mixed and then simultaneously spin coated onto the silicon substrate. On the other hand, the sequential coating process first created a monolayer of a 900 nm nanosphere array on the silicon substrate, followed by the spin coating of another layer of a 100 nm colloidal array on top of the 900 nm array. The influence of the processing parameters, including the type of surfactant, spin speed, and spin time, on the self-assembly of the binary colloidal array were explored. The empirical outcomes show that by employing the optimal processing conditions, binary colloidal arrays can be achieved by both the concurrent and sequential spin coating processes.

Aggregation kinetics of binary systems containing kaolinite and Pseudomonas putida induced by different 1:1 electrolytes: specific ion effects

Background The interactions between colloidal particles in the binary systems or mixture colloids containing clay minerals and bacteria have important influences on formations and stabilities of soil aggregates, transportations of soil water, as well as biological activities of microorganisms. How the interfacial reaction of metal ions affects their interaction therefore becomes an important scientific issue. Methods Dynamic light scattering studies on the aggregation kinetics of mixture colloids containing kaolinite and Pseudomonas putida (P. putida) were conducted in this study. Results Aggregation could be observed between kaolinite and kaolinite, between kaolinite and P. putida when P. putida content was less than 33.3%. Additionally, aggregation rates decreased with increasing P. putida content. The critical coagulation concentrations and activation energies indicated that there were strong specific ion effects on the aggregation of mixture colloids. Most importantly, the activation energy increased sharply with increasing P. putida content, which might result from the lower Hamaker constant of P. putida compared with that of kaolinite. Contributions (1) Strong specific ion effects on mixture colloids aggregation of kaolinite-P. putida were observed; (2) the aggregation behavior of mixture colloids was determined by the average effects of mixture colloids, rather than the specific component. This finding provides an important methodological guide for further studies on the colloidal aggregation behavior of mixture systems with organic and inorganic materials.

Anomalous Long-Range Attraction in Colloidal Binary Mixtures at Fluid–Fluid Interfaces

The properties of binary colloidal systems have gained the interest of researchers because they have much richer structures than their one-component counterpart. Continuing efforts are being made on the theoretical side on binary colloidal systems, while many issues remained unsolved for the lack of solid experimental supports, especially for study in the field of two-dimensional (2D) binary colloids system. Oil–water interfaces can serve as a good stringent 2D confinement for colloidal particles and can avoid anomalous problems caused by the quasi-two-dimensional environment in previous experimental reports. In this work, we conduct experimental research of binary colloids system in an oil–water interface to revisit theoretical predication. We measure an ultra-long-range attraction and discuss the possible mechanism of this attraction by comparing the experimental result with existing model and theory. This study could contribute more understanding of the binary colloidal system in both experimental aspects and theoretical aspects.

Superadiabatic demixing in nonequilibrium colloids

Dispersed colloidal particles that are set into systematic motion by a controlled external field constitute excellent model systems for studying structure formation far from equilibrium. Here we identify a unique demixing force that arises from repulsive interparticle interactions in driven binary colloids. The corresponding demixing force density is resolved in space and in time and it counteracts diffusive currents which arise due to gradients of the local mixing entropy. We construct a power functional approximation for overdamped Brownian dynamics that describes superadiabatic demixing as an antagonist to adiabatic mixing as originates from the free energy. We apply the theory to colloidal lane formation. The theoretical results are in excellent agreement with our Brownian dynamics computer simulation results for adiabatic, structural, drag and viscous forces. Superadiabatic demixing allows to rationalize the emergence of mixed, laned and jammed states in the system.

Synchronized fractionation and phase separation in binary colloids.

Fractionation is necessary for self-assembly in multicomponent mixtures. Here, reversible fractionation and crystallization are realized and studied in two-dimensional binary colloids which are supersaturated by enhancing the attraction between colloidal particles. As a deep and fast supersaturation results in gels with a uniform distribution of binary particles, a gradual quasistatic supersaturation process leads to a two-step crystallization in which small particles and large particles are fractionated as coexisting crystal and liquid phases respectively. Fractionation occurs as well in the quasistatic melting of gels. We show that the synchronized fractionation and phase separation arises from the competition between the size-dependent repulsion and the tunable attraction. The results in this study demonstrate a robust mechanism of fractionation via phase separation, and have important implication in understanding the reversible formation of membraneless organelles in living cells.

Crack density in bloodstains.

We construct a theoretical framework to understand the crack density of bloodstains by modeling whole blood as a suspension of binary size colloid particles. Our analysis based upon theories of soft capillarity and porous flows explains the observed increase of the crack density with increase of blood viscosity and decrease of environmental humidity. The results have direct implications on forensic science and medical diagnosis.

Length-scales of dynamic heterogeneity in a driven binary colloid.

Here we study the characteristic length scales in an aqueous suspension of a symmetric oppositely charged colloid subjected to a uniform electric field by Brownian dynamics simulations. We consider the in-plane structure in the presence of a sufficiently strong electric field where the like charges in the system form macroscopic lanes. We construct spatial correlation functions characterizing the structural order and that of particles of different mobilities in the plane transverse to the electric field at a given time. We call these functions equal time density correlation functions (ETDCFs). The ETDCFs between particles of different charges, irrespective of mobilities, are the structural ETDCFs, while those between particles of different mobilities are the dynamic ETDCFs. We extract the characteristic length of correlation by fitting the envelopes of the ETDCFs to exponential dependences. We find that the correlation length scales of the structural ETDCFs and the dynamic ETDCFs of the slow particles increase with time in a concurrent manner. This suggests that the clustering of particles tends to build up dynamically correlated slow particles in the plane transverse to the lanes. The ETDCFs can be measured for colloidal systems by directly following the particle motion by video-microscopy and may be useful to understand the patterns out of equilibrium.

Arsenic stabilization performance of a novel starch-modified Fe-Mn binary oxide colloid

Arsenic (As) is an environmentally hazardous contaminant and can be a serious threat to human health. In China, the remediation needs for a large number of As-contaminated sites renders a strong demand for efficient remedial reagents and cost-effective approaches. In this study, a novel starch-modified FeMn binary oxide (SFM), an amorphous colloidal material, has been synthesized as a remedial reagent and its As stabilization performance has been evaluated. A set of laboratory batch experiments were carried out with SFM of different dosages directly added into three contaminated soils to immobilize As. Results demonstrated that SFM could transform As in soil from non-specifically and specifically sorbed fractions to the more stable form bounded to amorphous iron hydrous oxides, thus reducing the As concentration in TCLP leachates by up to 93.2%. Results from adsorption tests and microscopic analysis indicated that the interactions between SFM and As are mainly controlled by adsorption, oxidation, and precipitation processes. SFM has abundant surface hydroxyl groups, with excellent adsorption properties for both As(V) and As(III), with the maximum adsorption capacities of 160.63 and 284.64 mg/g respectively at pH 7.0. The adsorption process closely fitted pseudo second-order kinetics and Freundlich isotherm model. SFM could increase soil Eh and oxidize As(III) to As(V), which facilitated the As stabilization in soil. Colloidal iron-based material directly used for stabilization in As contaminated soils is reported here for the first time. Starch modification improves both the reactivity and mobility of the stabilization agent in soil. Our findings propose an efficient and convenient reagent for As remediation in soil.

Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System.

Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (∼several tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

Explaining non-monotonic retention profiles during flow of size-distributed colloids

Non-monotonic retention profiles (NRP) have been observed in numerous studies of colloidal-nano flows in porous media. For the first time, we explain the phenomenon by distributed particle properties (size, shape, surface charge). We discuss colloidal-nano transport with fines attachment considering stochastically distributed filtration coefficient (particle attachment probability) and the area occupied by particle on the rock surface. The distributed dynamic system allows for exact averaging (upscaling) yielding a novel 3 × 3 system of equations for total concentrations. Besides the traditional equations of particle mass balance and capture-rate, the novel system contains a third independent equation for kinetics of site occupation during particle attachment. Ten laboratory tests exhibiting NRP have been successfully matched by the upscaled system for binary colloids. These laboratory tests with 7-parametric data arrays have been successfully matched by the 5-parameter model, which validates the model. The tuned parameter values belong to their common intervals. The laboratory data tuning was significantly simplified by deriving the exact solution of upscaled equations. These results provide valuable insights for understanding the transport mechanisms and environmental impact in colloidal-nano flows exhibiting NRP. Besides, the upscaled system and the analytical model for 1D transport facilitate interpretation of the laboratory coreflood data and allows for the laboratory-based predictions for 3D colloidal-nano transport at the field scale.

Stability of binary colloidal crystals immersed in a cholesteric liquid crystal.

In this paper, we model a number of both closed-packed and non-closed-packed crystals inside a cholesteric liquid crystal (LC) with different pitch values and nematic LC through the Landau-de Gennes free-energy method. We used binary boundary conditions (normal and planar anchoring) applied on the surface of colloids as we are interested in investigating the stability of binary crystals. The results indicate that body-centered-cubic (BCC) crystals have a lower-energy lattice defect structure than the diamond crystal, and the most energetically favorable BCC lattice can be formed in a cholesteric liquid crystal with a pitch value commensurate with the lattice spacing. Furthermore, it is shown that a pair of binary colloids can be self-assemble into a stable face-centered-cubic lattice structure inside a nematic LC, as it has the lowest energy comparing to diamond and BCC crystals.

Controlling the Surface Properties of Binary Polymer Brush-Coated Colloids via Targeted Nanoparticles.

This paper explores a novel mechanism for controlling the surface properties of polymer-coated colloids using targeted ("sticky") nanoparticles which attract monomers of certain polymer species. In our study, colloids are coated by two types of tethered polymer chains having different chemical properties. Attraction of nanoparticles to the monomers of one polymer type causes these polymer chains to contract toward the grafting surface, rendering the other type more exposed to the environment. Thus, the effective surface properties of the colloid are dominated by the intended polymer type. We use coarse-grained molecular dynamics (CGMD) simulation to demonstrate that introducing nanoparticles which interact preferentially with certain types of polymers makes it possible to switch between different surface properties of the colloid. This mechanism can in principle be exploited in drug delivery systems and self-assembly applications.

Breakdown of diffusivity\u2013entropy scaling in colloidal glass-forming liquids

Glass is a liquid that has lost its ability to flow. Why this particular substance undergoes such a dramatic kinetic slowdown yet remains barely distinguishable in structure from its fluid state upon cooling constitutes the central question of glass transition physics. Here, we investigate the pathway of kinetic slowdown in glass-forming liquids that consist of monolayers of ellipsoidal or binary spherical colloids. In contrast to rotational motion, the dynamics of the translational motion begin to violently slow down at considerably low area fractions (ϕT). At ϕT, anomalous translation–rotation coupling is enhanced and the topography of the free energy landscape become rugged. Based on the positive correlation between ϕT and fragility, the measurement of ϕT offers a novel method for predicting glassy dynamics, circumventing the prohibitive increase in equilibrium times required in high-density regions. Our results highlight the role that thermodynamical entropy plays in glass transitions.

Dielectrophoretic separation with a floating-electrode array embedded in microfabricated fluidic networks

In this study, we proposed a high-throughput separation strategy of the binary colloid mixture by dielectrophoresis (DEP) induced around large-scale bipolar electrode arrays embedded in microfabricated fluidic networks via a thorough numerical investigation. The usage of a floating electrode (FE) eliminates the need of external Ohmic connection to individual array units, therefore potentially steering the faddish design of new microdevice structures. Diffuse charge dynamics within the induced double layer at opposite ends of every FE permit a sinusoidal electric field to penetrate throughout the whole device, as long as the imposed field frequency is beyond the reciprocal resistor-capacitor time constant at the electrode/electrolyte interface. In this special device configuration, FEs interconnect multiple microchannels arranged in parallel. Pockets embedded on the sidewalls of fluidic channels help create strong field gradients at the tip of FEs and sharp pocket/channel junctions, improving the trapping performance of incoming bioparticles subjected to positive-DEP (pDEP) force, while latex beads experiencing negative-DEP (nDEP) stress are electrically squeezed to the midchannel and finally exit as a series of co-flowing thin streams with unequal translatory velocity. Taking the synergy of DEP force, induced-charge electro-osmosis, alternating-current electrothermal streaming, pressure-driven flow, and buoyancy effect into consideration, a numerical model is established to account for motion trajectories of micro-entities in full-scale three-dimensional space using the Lagrange particle track algorithm, as well as testing the feasibility of the device design in separation of the binary mixture containing yeast cells and polystyrene beads. Applying suitable voltage parameters of frequency O(1) MHz and electric field strength O(10) V/mm, highly efficient DEP separation is theoretically achievable under inlet flow velocity on the order of O(1) mm/s, where most of incoming yeasts are captured by pDEP within these five parallel branching channels, while polystyrene spheres are repelled by nDEP away from the FE array to form slim beams co-flowing into the outlet according to the calculation results. The microfluidic separation device exploiting the FE array offers great potential to build up scalable electrokinetic platforms for high-throughput on-chip sample treatment.

Photoinduced electron transfer in semiconductor–clay binary nanosheet colloids controlled by clay particles as a turnout switch

Although semiconductor photocatalysis has been investigated actively for a long time, control of dark processes successive to electron transfer from photocatalysts is almost unexplored compared with designing photocatalysts themselves. The present study proposes employment of clay particles as for controlling the dark processes independently of semiconductor photocatalyst particles. We employed niobate–clay binary nanosheet colloids, where colloidal niobate and clay nanosheets are spatially separated at a micrometer level. Niobate nanosheets worked as the semiconductor photocatalyst that released electrons upon UV excitation, and clay nanosheets worked as the turnout switch of the released electrons to determine their destination. When methylviologen (MV2+) molecules that accept the electrons released from niobate were adsorbed on clay nanosheets, reduction of MV2+ predominantly occurred, and hydrogen was little evolved from the colloid. When Pt nanoparticles were deposited on clay nanosheets, photocatalytic hydrogen evolution occurred because Pt loaded on the clay nanoparticles played a role of cocatalyst. When MV2+ and Pt were co-loaded on clay nanosheets, both of MV2+ reduction and hydrogen evolution occurred competitively. The photocatalytic hydrogen evolution carried out by stirring the colloid sample was worse than that conducted without stirring, which indicated positive contribution of the spatial separation of photocatalytic niobate and cocatalytic clay nanosheets.

Random lasing from dyed polystyrene spheres in disordered environments

Advance designs of random lasers toward the development of miniature laser systems are in demand. Random lasing from Rhodamine-B dye doped polystyrene microparticles was demonstrated. Bare polystyrene spheres were used as scatterers, and these provided optical feedback to the gain. Random lasing was successfully demonstrated in two different disordered environments: in binary colloidal solution and in photonic glass. Incoherent feedback occurred in both the cases, and laser emission was obtained with a spectral line width of ∼10 nm. Optimized number densities of bare and dye doped polystyrene microparticles required for random lasing action in such systems were evaluated. Although both disordered media showed random lasing with similar number densities of the microparticles, the lasing threshold in the case of photonic glass was lower in comparison to binary colloidal solution. This was because of higher index contrast and larger filling fraction of microparticles in the case of photonic glass. Lasing results obtained for photonic glass were compared with their previous results of Bloch lasing in photonic crystal synthesized using similar dye doped polystyrene microparticles.

Pattern Formation in Binary Colloidal Assemblies: Hidden Symmetries in a Kaleidoscope of Structures

In this study, we present a detailed investigation of the morphology of binary colloidal structures formed by self-assembly at air/water interface of particles of two different sizes, with a size ratio such that the larger particles do not retain a hexagonal arrangement in the binary assembly. While the structure and symmetry of binary mixtures in which such hexagonal order is preserved has been thoroughly scrutinized, binary colloids in the regime of nonpreservation of the hexagonal order have not been examined with the same level of detail due also to the difficulty in finding analysis tools suitable to recognize hidden symmetries in seemingly amorphous and disordered arrangements. For this purpose, we resorted to a combination of different analysis tools based on computational geometry and computational topology to get a comprehensive picture of the morphology of the assemblies. By carrying out an extensive investigation of binary assemblies in this regime with variable concentration of smaller particles with respect to larger particles, we identify the main patterns that coexist in the apparently disordered assemblies and detect transitions in the symmetries upon increase in the number of small particles. As the concentration of small particles increases, large particle arrangements become more dilute and a transition from hexagonal to rhombic and square symmetries occurs, accompanied also by an increase in clusters of small particles; the relative weight of each specific symmetry can be controlled by varying the composition of the assemblies. The demonstration of the possibility to control the morphology of apparently disordered binary colloidal assemblies by varying experimental conditions and the definition of a route for the investigation of disordered assemblies are important for future studies of complex colloidal patterns to understand self-assembly mechanisms and to tailor the physical properties of colloidal assemblies.

Composition inversion in mixtures of binary colloids and polymer.

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple." Here, we consider a very simple mixture of two colloidal and one non-adsorbing polymer species, which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion-a maximum in the large particle concentration in the liquid phase. Close to criticality, the density fluctuations are found to be dominated by the larger colloids.

Magneto-optical properties of binar ferrocolloids

In this work, a new method for increasing optical anisotropy of a ferrocolloid through introducing the coiled polymer molecules or elongated nanosized non-magnetic particles is realized. Since the dimensions of structural elements comprising such a binary colloidal solution are small compared to the wavelength, the ferrocolloid remains optically homogeneous. Type I binary ferrocolloids are obtained by introducing polybutadiene molecules into a magnetic fluid (magnetite + kerosene + oleic acid). In this case, an increase in the double refraction (DR) is due to the deformation and stretching of the polymer coils along the magnetic field. In weak fields, double amplification of the signal was detected for the concentration of polymer molecules of about 0.5 %. A further increase in the concentration of impurity molecules weakens DR due to a disturbance of the sedimentation stability of the solution and precipitation of colloidal particles. Type II binary solution is synthesized on the basis of a magnetic fluid and rod-shaped impurity nanoparticles of goethite ( αFeOOH). The transverse dimension of the impurity particles (10 − 30 nm) was close to the average diameter of single-domain magnetite particles, and the longitudinal dimension was an order of magnitude larger. An increase in the DR occurs due to the orientation of long axes of impurity particles along the magnetic field caused by the difference in the ”demagnetizing” coefficients along and across the axis of the particle. The magnetic double refraction has been studied depending on the concentration of magnetite and impurity particles and the strength of the magnetic field. For the first time, an experimental substantiation of the multiple amplification of the DR signal by impurity particles was obtained. In the fields (up to 10 kA/m) and for the volume fraction of impurity particles of the order of one percent, the DR signal is amplified by more than an order of magnitude. In stronger fields, the signal gain, associated with the influence of impurity particles, reaches saturation and, with further increase in the field strength, remains practically unchanged, while the total anisotropy of the solution continues to increase due to the orientation of the magnetite particles.

Transient dynamical responses of a charged binary colloid in an electric field.

In a model system of oppositely charged colloids we study via Brownian dynamics simulation the dynamical response as the system approaches steady states upon application of a constant electric field. The system is known to form patterns of like charges in the transverse plane to the field that are elongated along the field as lanes. We show that an increase in structural heterogeneity leads to non-Gaussian tails in the probability distribution of particle displacements [self van Hove functions (self-vHfs)]. The self-diffusion coefficient depends upon the time of the observations and consequently indicates aging in the system. However, the anomalies in the self-vHfs and diffusion do not appear during the melting of the structures.