Now showing 1 - 6 of 6
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Synthesis of non-spherical patchy particles at fluid-fluid interfaces: via differential deformation and their self-assembly

01-01-2016, Sabapathy, Manigandan, Shelke, Yogesh, Basavaraj Madivala Gurappa, Ethayaraja Mani

Non-spherical patchy particles are potential candidates as building blocks for the design of target colloidal structures via spontaneous self-organization. We report a facile scheme to synthesize non-spherical particles with patchy electrostatic interactions. In this method, charged spherical latex particles such as polystyrene (PS) are deformed unequally at an oil-water interface due to heating and partial swelling. The spherical particles then evolve into non-spherical shapes such as 'acorn-like' and 'idly-like'. We explain the mechanism of differential deformation by comparing the heat of viscous dissipation and the interfacial energies. Furthermore, if oppositely charged additives such as the cetyltrimethylammonium bromide (CTAB) surfactant or silica nanoparticles are present in water (subphase), electrostatic attraction leads to adsorption of these species on the PS surface exposed to water. As a result, one side of the particles is selectively functionalized, while the other side remains unaltered. As the latex particles are negatively charged initially, this method yields particles that are non-spherical in shape and with negative charges on one side and positive charges on the other side. The degree of shape deformation and patch coverage can be varied by choosing different surface active additives. We extend this approach to curved interfaces and demonstrate a high throughput emulsion based approach for the synthesis of such particles. Self-assembly of these particles shows interesting structures such as linear, branched polymeric or worm-like chains and micelle-like spherical aggregates. These shape anisotropic particles with orientation specific interactions that mimic bio-macromolecular systems can be further explored for self-assembly into hierarchical mesoscale structures.

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Exploiting Heteroaggregation to Quantify the Contact Angle of Charged Colloids at Interfaces

21-06-2022, Sabapathy, Manigandan, Md, Khalid Zubair, Kumar, Hemant, Ramamirtham, Sashikumar, Ethayaraja Mani, Basavaraj Madivala Gurappa

We exploit the aggregation between oppositely charged particles to visualize and quantify the equilibrium position of charged colloidal particles at the fluid-water interface. A dispersion of commercially available charge-stabilized nanoparticles was used as the aqueous phase to create oil-water and air-water interfaces. The colloidal particles whose charge was opposite that of the nanoparticles in the aqueous phase were deposited at the chosen fluid-water interface. Heteroaggregation, i.e., aggregation between oppositely charged particles, leads to the deposition of nanoparticles onto the larger particle located at the interface; however, this only occurs on the surface of the particle in contact with the aqueous phase. This selective deposition of nanoparticles on the surfaces of the particles exposed to water enables the distinct visualization of the circular three-phase contact line around the particles positioned at the fluid-water interface. Since the electrostatic association between the nanoparticles and the colloids at interfaces is strong, the nanoparticle assembly on the larger particles is preserved even after being transferred to solid substrates via dip-coating. This facilitates the easy visualization of the contact line by electron microscopy and the determination of the equilibrium contact angle of colloidal particles (θ) at the fluid-water interface. The suitability of the method is demonstrated by the measurement of the three-phase contact angle of positively and negatively charged polystyrene particles located at fluid-water interfaces by considering particles with sizes varying from 220 nm to 8.71 μm. The study highlights the effect of the size ratio between the nanoparticles in the aqueous phase and the colloidal particles on the accuracy of the measurement of θ.

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Synthesis of single and multipatch particles by dip-coating method and self-assembly thereof

03-02-2015, Sabapathy, Manigandan, Christdoss Pushpam, Sam David, Basavaraj Madivala Gurappa, Ethayaraja Mani

We report a simple strategy to produce single and multipatch particles via the conventional dip-coating process. In this method, a close-packed monolayer of micron-sized silica particles is first formed at air-polymer solution interface, followed by dip coating of particles on a glass substrate. The simultaneous deposition of both polymer and particles on the substrate gives rise to a thin polymer layer and a monolayer of silica particles. Sonication of the substrate leads to the formation of a polymeric patch on one side of the particles. The patch shape depends on the aging of the polymer film prior to sonication. With aging time the patch evolves from ring-like to disk-like. This technique allows easy control of patch width by varying the concentration of polymer in the solution. We further show that the number of patches on the particle can be increased by controlling the concentration of silica particles at the interface such that surface coverage is less than that required for the formation of a close-packed monolayer. The single and multipatch particles are characterized by scanning electron and optical microscopy for the patch size, shape, and number distribution. The as-synthesized particles are used as a model to study self-assembly of colloids with electrostatic repulsion and patchy hydrophobic attractions due to polymeric patches. We find the formation of doublets and finite-sized clusters due to patchy interactions. Dip coating can be automated to produce large quantities of patchy particles, which is one of the major limitations of other methods of producing patchy particles.

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Staggered Linear Assembly of Spherical-Cap Colloids

11-07-2017, Shelke, Yogesh, Sabapathy, Manigandan, Mani, Ethayaraja

Linear assembly of colloidal particles is of fundamental interest in visualizing polymer dynamics and living organisms. We have developed a fluid-fluid interface-based method to synthesize spherical-cap polymeric latex particles. These particles are shown to spontaneously self-assemble in zigzag arrangement. The linear assembly is induced due to the shape anisotropy (one side is curved and the other side is nearly flat) and heterogeneous charge distribution on the particle surfaces. The necessities of these conditions are justified within the framework of DLVO theory. Spherical-cap particles of various size and aspect ratio reproduced the observed linear assembly, thus demonstrating the robustness of the self-assembly mechanism. While these types of assemblies are observed in spherical particles using microfluidic devices or electric field, the proposed approach is rather facile and does not require any external field. These novel assemblies could be potentially useful to understand kinetics of nucleation and growth of amyloidogenic proteins and to prepare artificial swimming microorganisms.

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Self-assembly of inverse patchy colloids with tunable patch coverage

01-01-2017, Sabapathy, Manigandan, Ann Mathews K, Remya, Ethayaraja Mani

We report a simple and scalable technique for the preparation of patchy particles with tunable patch coverage. These particles are categorized as inverse patchy colloidal particles (IPCs) as the patches repel each other while patch and non-patch surfaces attract. We demonstrate the effect of patch coverage, concentration of electrolyte and concentration of particles on the self-assembly of IPC particles. The study identifies various clustering zones such as (1) finite-sized clusters, (2) chain-like assemblies and (3) irregular amorphous aggregates. The linear assemblies are observed over a wide range of particle concentrations and salt concentrations. The anisotropic electrostatic interaction controls the formation of chain-like assemblies. In an extended study, we use negatively charged isotropic colloidal (NCIC) particles to tune the self-assembly of IPC particles. Interestingly, we observe significant improvement in the clustering efficiency of IPC particles leading to the formation of co-polymeric, flexible branched chains. Depending on the number ratio of NCIC particles with respect to IPC particles, the clustering process is classified into three different phases such as (1) finite-sized, (2) linear and (3) dispersed state. Using a quantitative analysis we show that such evolution of structures is attributed to seeding and crowding effects caused by the addition of NCIC particles. The use of NCIC particles thus control the self-assembly of inverse patchy colloids and tune the number and shape of the self-assembled structures.

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Visualization of the equilibrium position of colloidal particles at fluid-water interfaces by deposition of nanoparticles

07-09-2015, Sabapathy, Manigandan, Kollabattula, Viswas, Basavaraj Madivala Gurappa, Ethayaraja Mani

We present a general yet simple method to measure the contact angle of colloidal particles at fluid-water interfaces. In this method, the particles are spread at the required fluid-water interface as a monolayer. In the water phase a chemical reaction involving reduction of a metal salt such as aurochloric acid is initiated. The metal grows as a thin film or islands of nanoparticles on the particle surface exposed to the water side of the interface. Analyzing the images of particles by high resolution scanning microscopy (HRSEM), we trace the three phase contact line up to which deposition of the metal film occurs. From geometrical relations, the three phase contact angle is then calculated. We report the measurements of the contact angle of silica and polystyrene (PS) particles at different interfaces such as air-water, decane-water and octanol-water. We have also applied this method to measure the contact angle of surfactant treated polystyrene particles at the air-water interface, and we find a non-monotonic change of the contact angle with the concentration of the surfactant. Our results are compared with the well-known gel trapping technique and we find good comparison with previous measurements.