Soft colloidal monolayers with reflection symmetry through confined drying.

Colloidal monolayers serve as fundamental building blocks in fabricating diverse functional materials, pivotal for surface modifications, chemical reactivity, and controlled assembly of nanoparticles. In this article, we report the formation of colloidal monolayers generated by drying an aqueous droplet containing soft colloids confined between two hydrophilic parallel plates. The analysis of the kinetics of evaporation in this confined mode showed that: (i) for a significant portion of the drying time, the drops adopt a catenoid configuration; (ii) in the penultimate stage of drying, the catenoid structure undergoes division into two daughter droplets; (iii) the three-phase contact line remains pinned at a specific location while it continuously slips at all other locations. The interplay between interface-assisted particle deposition onto the solid substrate and the time evolution of particle concentration within the droplet during evaporation results in unique microstructural features in the deposited patterns. Notably, these deposit patterns exhibit reflection symmetry. The microstructural features of the dried deposits are further quantified by calculating the particle number density, inter-particle separation, areal disorder parameter, and bond orientational order parameter. The variation of these parameters for deposits formed under different conditions, such as by altering the spacing between parallel plates and the concentration of microgel particles in the droplet, is discussed.

Responsive soft actuator: harnessing multi-vapor, light, and magnetic field stimuli.

Bioinspired soft actuators, capable of undergoing shape deformation in response to external triggers, hold great potential in fields such as soft robotics, artificial muscles, drug delivery, and smart switches. However, their widespread application is hindered by limitations in responsiveness, durability, and complex fabrication processes. In this study, we propose a new approach to tackle these challenges by developing a single-layer soft actuator that responds to multiple stimuli using a straightforward solution-casting method. This actuator comprises bio-polymer gelatin, bio-compatible PEDOT:PSS, and iron oxide (Fe3O4) nanoparticles. Our actuator exhibits responsiveness to a range of organic solvent vapors, including water vapor, light, and magnetic fields. Notably, it exhibits rapid and reversible bending in distinct directions in response to different vapors, bending upwards in the presence of water vapor and downwards in the presence of alcohol vapor. Moreover, exposure to infrared (IR) light induces a bending toward the light source. The incorporation of magnet-responsive Fe3O4 nanoparticles induces multi-functionality in the actuator. The actuation characteristics of the actuator are controlled by leveraging its responsiveness to dual stimuli, such as water vapor and magnetic fields, as well as light and magnetic fields. For the proof of concept, we showcase several potential applications of our multi-stimuli responsive soft actuator, including magnet-triggered electrical switches, cargo transportation, soft grippers, targeted drug delivery, energy harvesting, and bio-mimicry.

High-Performance Printed Ag2Se/PI Flexible Thermoelectric Film for Powering Wearable Electronics.

We report the magnificent thermoelectric properties of the n-type Ag2Se film printed onto a flexible polyimide (PI) substrate. The orthorhombic ß-Ag2Se phase of the processed Ag2Se film is confirmed from the X-ray diffractogram. Remarkably, the resulting Ag2Se/PI film exhibits outstanding thermoelectric properties, boasting maximum power factors of 1.4 and 2.1 mW/mK2 at 300 and 405 K, respectively. Furthermore, the flexibility of the Ag2Se/PI film remains intact even after undergoing 1500 bending cycles with no degradation observed in its thermoelectric performance. To demonstrate the practical application of our findings, a flexible thermoelectric prototype is constructed using the fabricated Ag2Se/PI films, which can harvest an impressive output voltage of 52 mV across a temperature difference of 53 K. Additionally, the prototype generates a maximum power output of 7.2 µW with a 40 K temperature difference and can produce 13 mV output voltage when subjected to around a 10 K temperature gradient when the cold side temperature is maintained at 308 K. Moreover, leveraging body heat with just a 1 K temperature variance between the body and the surrounding environment, the prototype could yield an impressive voltage output of 1.6 mV, marking the highest reported voltage output from human body heat to date. Our study not only introduces a cost-effective method for producing high-performance flexible thermoelectric films but also highlights their potential applications in wearable and implantable electronics.

Determining the Characteristics of Ultrathin Polymer Films: A Spectroscopic Ellipsometry Approach.

Ellipsometry is a powerful and convenient technique that is widely used to determine the thickness and optical characteristics of polymer thin films. The determination is accomplished by modeling the measured change in the polarization of an electromagnetic wave upon interacting with the thin film. However, due to the strong statistical correlations between the fit parameters in the model, simultaneous determination of the thickness and the refractive indices of optically anisotropic ultrathin films using ellipsometry remains a challenge. Here, we propose an approach that can be used to obtain reliable values of both the thickness and the optical anisotropy of ultrathin polymer films. The approach was developed by performing spectroscopic ellipsometry measurements on thin films of hydrophobic polystyrene and hydrophilic chitosan of thickness between a few tens to a few hundred nm and whose absolute value of the birefringence differed by approximately an order of magnitude. Careful consideration of the characteristics of the root mean squared error of the fits obtained by modeling the ellipsometry data and the statistical correlations between the fit parameters formed the basis of the proposed approach.

Contact Angle Modulation: In Situ Polymer Deposition during Sessile Drop Evaporation.

The drying kinetics of a sessile drop on a solid surface are a widely studied phenomenon because of their relevance to various fields such as coating, printing, medical diagnostics, sensing, and microfluidic technology. Typically, the drop undergoes drying either at a constant contact radius (R) with a decrease in the three-phase contact angle or at a constant contact angle (θ) with a reduction in the radius with time. These two drying modes are referred to as CCR and CCA, respectively. It is not uncommon where both R and θ may decrease during drying, especially in the penultimate stage of drying. In this work, we report a scenario wherein the θ increases while R decreases during the drying process of an aqueous polymer solution on a high surface energy substrate. This behavior is observed across different polymer systems (such as poly(ethylene oxide) and polyvinyl pyrrolidine), varying molecular weights, and polymer concentrations. As the drop dries, the polymer gets deposited at the three-phase contact line, thus reducing the surface energy of the substrate and leading to an increase in the contact angle. The drop responds by attempting to reach a new equilibrium contact angle through slipping. The temporal increase in contact angle follows a power law scaling behavior. This study demonstrates an in situ modulation of contact angle facilitated by evaporation and polymer deposition, showcasing unconventional drying dynamics.

Vapor and Light Responsive Biocompatible Soft Actuator.

Bioinspired smart polymeric materials that undergo three-dimensional shape deformation in response to specific stimuli have gained significant attention in the field of soft robotics and intelligent devices. Despite the substantial advancements in soft robotics, there is a growing demand for the design of multistimuli-responsive soft actuators using a single layer of material due to its reduced complexity and ease of manufacturing and durability. Here, we report the actuation characteristics of a single-layer, dual-responsive soft actuator that overcomes the commonly encountered delamination issues often associated with bilayer systems by incorporating PEDOT:PSS with cassava starch. This soft actuator exhibits deformations in response to various solvent vapors, such as water, alcohol, and acetone. Remarkably, it demonstrates opposite deformations upon exposure to water and alcohol vapors. Additionally, the actuator responds to light triggers and folds upon exposure to sunlight and infrared light. The degree of folding can be precisely controlled by adjusting the intensity of the light source. Furthermore, the periodic geometric patterns imposed on the surface of the actuator provide an additional handle to control the bending axis. For proof of concept, we leverage the actuation capabilities of our actuator to showcase a range of potential applications, including its usage in wearable textiles, crawler robots, smart curtains, push-and-pull machines, and smart lifts.

Probing the thermoelectric properties of aluminium-doped copper iodide.

Copper iodide, an environmentally friendly material abundant in nature, holds great significance for room temperature thermoelectric (TE) applications owing to its high Seebeck coefficient and optical transparency. However, to fully unlock its thermoelectric potential and match the performance of conventional TE materials, there is a need to further enhance its electrical conductivity. In this study, we have successfully synthesized nano-crystalline powders of both undoped and aluminium-doped CuI at room temperature using the chemical precipitation method in an ethanol medium. The concentration of aluminium dopant has been optimized to maximize TE performance. At 400 K, the highest TE power factor and figure of merit achieved are 79 µW m-1 K-2 and 0.08, respectively, for CuI doped with 0.1 mol% Al. This enhancement in TE properties can be attributed to the increased carrier density resulting from aluminium doping. The impact of aluminium doping on the temperature-dependent thermal conductivity has been investigated, and the findings are explained by the decay mechanism of optical phonons, supported by the anharmonic phonon coupling theory. Our work delves into the evolution of structural, thermal, optical, and TE properties of CuI upon aluminium (Al) doping. The results provide valuable insights into the future application of CuI in transparent thermoelectric and optoelectronic fields.

Morphologies of electric-field-driven cracks in dried dispersions of ellipsoids.

We report an experimental and theoretical study of the morphology of desiccation cracks formed in deposits of hematite ellipsoids dried in an externally applied alternating current (ac) electric field. A series of transitions in the crack morphology is observed by modulating the frequency and the strength of the applied field. We also found a clear transition in the morphology of cracks as a function of the aspect ratio of the ellipsoid. We show that these transitions in the crack morphology can be explained by a linear stability analysis of the equation describing the effective dynamics of an ellipsoid placed in an externally applied ac electric field.

Multivapor-Responsive Controlled Actuation of Starch-Based Soft Actuators.

Multivapor-responsive biocompatible soft actuators have immense potential for applications in soft robotics and medical technology. We report fast, fully reversible, and multivapor-responsive controlled actuation of a pure cassava-starch-based film. Notably, this starch-based actuator sustains its actuated state for over 60 min with a continuous supply of water vapor. The durability of the film and repeatability of the actuation performance have been established upon subjecting the film to more than 1400 actuation cycles in the presence of water vapor. The starch-based actuators exhibit intriguing antagonistic actuation characteristics when exposed to different solvent vapors. In particular, they bend upward in response to water vapor and downward when exposed to ethanol vapor. This fascinating behavior opens up new possibilities for controlling the magnitude and direction of actuation by manipulating the ratio of water to ethanol in the binary solution. Additionally, the control of the bending axis of the starch-based actuator, when exposed to water vapor, is achieved by imprinting-orientated patterns on the surface of the starch film. The effect of microstructure, postsynthesis annealing, and pH of the starch solution on the actuation performance of the starch film is studied in detail. Our starch-based actuator can lift 10 times its own weight upon exposure to ethanol vapor. It can generate force ∼4.2 mN upon exposure to water vapor. To illustrate the vast potential of our cassava-starch-based actuators, we have showcased various proof-of-concept applications, ranging from biomimicry to crawling robots, locomotion near perspiring human skin, bidirectional electric switches, ventilation in the presence of toxic vapors, and smart lifting systems. These applications significantly broaden the practical uses of these starch-based actuators in the field of soft robotics.

Effect of Colloidal Surface Charge on Desiccation Cracks.

We report the effect of polarity and surface charge density on the nucleation and growth kinetics of desiccation cracks in deposits of colloids formed by drying. We show that the average spacing between desiccation cracks and crack opening are higher for the deposit of positively charged colloids than that of negatively charged colloids. The temporal evolution of crack growth is found to be faster for positively charged particle deposits. The distinct crack patterns and their kinetics are understood by considering the spatial arrangement of particles in the deposit, which is strongly influenced by the substrate-particle and particle-particle interactions. Interestingly, the crack spacing, the crack opening, and the rate at which the crack widens are found to increase upon decreasing the surface charge of the colloids.

Probing the tightly bound layer in poly(vinyl alcohol) thin films using swelling measurements.

A strongly adsorbed, tightly bound polymer layer can exist at the polymer/substrate interface in polymer thin films and polymer nanocomposites. The characteristics of the tightly bound layer have long been of interest because of its effect on physical properties. However, direct investigations are challenging as the layer is buried deep within the sample. A common approach to access the tightly bound layer is by rinsing or washing away the loosely bound polymer using a good solvent. While this enables direct investigations of the tightly bound layer, it is unclear if the layer remains unperturbed by the preparation process. Therefore, in situ techniques that can probe the tightly bound layer without strongly perturbing it are preferable. In previous work (P. D. Lairenjam, S. K. Sukumaran and D. K. Satapathy, Macromolecules, 2021, 54, 10931-10942), we introduced an approach to estimate the thickness of the tightly bound layer at the chitosan/silicon interface using swelling of nanoscale thin films when exposed to solvent vapour. To determine the general validity of the approach, in this work we investigated the swelling of poly(vinyl alcohol) (PVA) thin films using two independent techniques: spectroscopic ellipsometry and X-ray reflectivity. We found that the swelling kinetics for thin films of initial thickness in the range 18-215 nm could be described by a single time-dependent swelling ratio, c(t), provided we account for a tightly bound layer of thickness 15 nm at the polymer/substrate interface. Consistent with the conclusions from the swelling measurements, electron density profiles determined by modeling X-ray reflectivity data clearly indicated the existence at the polymer/substrate interface of a 15 nm thick layer of a slightly higher density than the rest of the film. The early-time diffusion coefficient of H2O in PVA determined from the temporal evolution of the mass uptake of the solvent vapour was found to decrease by 3-4 orders of magnitude when the film thickness decreased by approximately an order of magnitude.

Enhanced Thermoelectric Efficiency in P-Type Mg3Sb2: Role of Monovalent Atoms Codoping at Mg sites.

Due to natural abundance, low cost, and compatibility with sustainable green technology, Mg3Sb2-based Zintl compounds are comprehensively explored as potential thermoelectric materials for near-room temperature applications. The effective use of these materials in thermoelectric devices requires both p and n-type Mg3Sb2 having comparable thermoelectric efficiency. However, p-type Mg3Sb2 has inferior thermoelectric efficiency efficiency compared to its n-type counterpart due to low electrical conductivity (∼103Sm-1). Here, we show that codoping of monovalent atoms (Li-Ag, and Na-Ag) at the Mg site of Mg3Sb2 produces a synergistic effect and boosts the electrical conductivity, which enhances the thermoelectric properties of p-type Mg3Sb2. While, Ag prefers to occupy the Mg2 site, Li and Na are favorable at the Mg1 site of Mg3Sb2 lattice. Compared to Li-Ag codoping, Na-Ag codoping in Mg3Sb2 is found to be more effective for increasing the charge carrier concentration and significantly augmenting the electrical conductivity. The dominance of the three-phonon scattering mechanism in Li and Li-Ag doped Mg3Sb2 and the four-phonon scattering process for the Na and Na-Ag doped Mg3Sb2 are confirmed. Due to the simultaneous increase in electrical conductivity and decrease in thermal conductivity, the zT value ∼0.8 at 675 K achieved for Mg2.975Na0.02Ag0.005Sb2 is the highest value among p-type Mg3Sb2. Our work shows a constructive approach to enhance the zT of p-type Mg3Sb2 via monovalent atoms codoping at the Mg sites.

Depletion zone in two-dimensional deposits of soft microgel particles.

HYPOTHESIS: Microgels are a class of model soft colloids that act like surfactants due to their amphiphilicity and are spontaneously adsorbed to the fluid-air interface. Here, we exploit the surfactant-like characteristics of microgels to generate Marangoni stress-induced fluid flow at the surface of a drop containing soft colloids. This Marangoni flow combined with the well-known capillary flow that arises during the evaporation of a drop placed on a solid surface, leads to the formation of a novel two-dimensional deposit of particles with distinct depletion zones at its edge. EXPERIMENTS: The evaporation experiments using sessile and pendant drops containing microgel particles were carried out, and the microstructure of the final particulate deposits were recorded. The kinetics of the formation of the depletion zone and its width is studied by tracking the time evolution of the microgel particle monolayer adsorbed to the interface using in situ video microscopy. FINDINGS: The experiments reveal that the depletion zone width linearly increases with droplet volume. Interestingly, the depletion zone width is larger for drops evaporated in pendant configuration than the sessile drops, which is corroborated by considering the gravitational forces exerted on the microgel assembly on the fluid-air interface. The fluid flows arising from Marangoni stresses and the effect of gravity provide novel ways to manipulate the self-assembly of two-dimensional layers of soft colloids.

Triple-line dynamics of a soft colloid-laden drop on a hydrophobic surface.

Evaporation of fluid from a pinned drop placed on solid surface proceeds via constant contact radius (CCR) mode, with a continuous reduction in the contact angle. The reduction of contact angle leads to an imbalance of interfacial tensions at the three-phase contact line. When the unbalanced force is sufficiently strong, the drop slips from the pinned contact line and slides inward. Depinning of the drop alters the mode of evaporation to constant contact angle (CCA) mode till it repins onto the surface. The change in evaporation mode from CCR to CCA is usually achieved by tuning the pinning energy barrier by controlling the surface properties of the substrate. Here, we demonstrate that the evaporation mode can be controlled by solely tailoring the surface tension of the drop, which is achieved in microgel particle-laden sessile drops that show spontaneous adsorption of microgels to the air/water interface, leading to a decrease in the interfacial tension. We show that droplets containing a sufficient number of microgels evaporate predominantly in CCR mode even on a hydrophobic surface, and the contact line remains pinned throughout the evaporation of the drop. Interestingly, the contact line dynamics can be controlled by tuning the softness of the microgels and the particle concentration in the drops.

Intrinsic-water desorption induced thermomechanical response of hydrogels.

We report an interplay between the desorption of intrinsic water and relaxation of polymer chains resulting in an unusual thermomechanical response of a hydrogel, wherein the elastic modulus increases in a certain temperature range followed by a sharp decrease with a further increase in temperature. We establish that, in a hydrogel, the desorption of disparate water types having distinct binding energy affects the consolidation and relaxation behaviour of the matrix, which in turn affects the mechanical properties at different temperature ranges. Using temperature-dependent dielectric relaxation spectroscopy and nanoindentation techniques, the chain dynamics and mechanical properties are investigated.

Giant Thermoelectric Efficiency of Single-Filled Skutterudite Nanocomposites: Role of Interface Carrier Filtering.

The advantage of secondary-phase induced carrier filtering on the thermoelectric properties has paved the way for developing cost-effective, highly efficient thermoelectric materials. Here, we report a very high thermoelectric figure-of-merit of skutterudite nanocomposites achieved by tailoring interface carrier filtering. The single-filled skutterudite nanocomposites are prepared by dispersing rare-earth oxides nanoparticles (Yb2O3, Sm2O3, La2O3) in the skutterudite (Dy0.4Co3.2Ni0.8Sb12) matrix. The nanoparticles/skutterudite interfaces act as efficient carrier filters, thereby significantly enhancing the Seebeck coefficient without compromising the electrical conductivity. As a result, the highest power factor of ∼6.5 W/mK2 is achieved in the skutterudite nanocomposites. The nonuniform strain distribution near the nanoparticles due to the local lattice misfit and concentration fluctuations affect the heat carriers and thereby reduce the lattice thermal conductivity. Moreover, the three-dimensional atom probe analysis reveals the formation of Ni-rich grain boundaries in the skutterudite matrix, which also facilitates the reduction of lattice thermal conductivity. Both the factors, i.e., the reduction in lattice thermal conductivity and the enhancement of the power factor, lead to an enormous increase in ZT up to ∼1.84 at 723 K and an average ZT of about 1.56 in the temperature range from 523 to 723 K, the highest among the single-filled skutterudites reported so far.

Thermoelectric properties of Ag-doped CuI: a temperature dependent optical phonon study.

Due to the natural abundance and non-toxicity of copper (Cu) and iodine (I), γ-CuI has been widely explored as a potential transparent thermoelectric material for near room temperature applications. Here, we report the effect of doping of an heavy atom such as silver (Ag) on the evolution of temperature-dependent optical phonon modes and thermoelectric properties of chemically synthesized single-phase nanocrystalline γ-CuI. We found that Ag doping reduces the lattice parameters of CuI and thereby confirms the occupancy of Ag atoms at the vacancy sites of CuI. The decrease in phonon lifetime with the increase in temperature, which strongly influences the lattice thermal conductivity, is established from temperature-dependent optical phonon vibrations study. The four-phonon/Umklapp scattering is found to be more prominent in undoped CuI, whereas three-phonon scattering is prominent in Ag-doped CuI. At low temperatures, an almost 90% increase in the Seebeck coefficient is observed for Ag-doped CuI compared to undoped CuI, which can be understood by taking into account a net decrease in the hole carrier concentration in doped CuI.

Effect of the Shape of the Confining Boundary and Particle Shape Anisotropy on the Morphology of Desiccation Cracks.

The control of the morphology of desiccation cracks is fascinating not only from the application point of view but also from the rich physics behind it. Here, we present a seemingly simple method to tailor the morphology of desiccation cracks by exploitation of the combined effect of particle shape anisotropy and the shape of the confining boundary. This allows us to make circular, square, and triangular-shaped desiccation cracks in the vicinity of the confining boundaries. As the colloidal dispersion dries in confined wells, a drying front appears at the center of the well. With further evaporation, the drying front recedes toward the boundary from the center of the well. We show that the temporal evolution of the drying front is strongly influenced by the shape of the well. Subsequently, desiccation cracks appear in the penultimate stage of drying, and the morphology of the cracks is governed by the shape of the drying front and hence by the shape of the wells. The spatial evolution of the crack pattern is quantified by estimation of the curvature of the cracks, which suggests that the influence of the confining boundary on crack formation is long-ranged. However, the cracks in the dried deposit consisting of spherical particles remain unaffected by the shape of the well, and the cracks are always radial. We establish a one-to-one correspondence between the shape of the drying front and the morphology of the crack pattern in the final dried deposit of ellipsoids.

Temporal evolution of viscoelasticity of soft colloid laden air-water interface: a multiple mode microrheology study.

Mechanical properties of particle laden interfaces is crucial for various applications. For water droplets containing soft microgel particles, passive microrheology studies have revealed that the dynamically varying surface area of the evaporating drop results in a viscous to viscoelastic transition along the plane of the interface. However, the behaviour of the medium orthogonal to the interface has been elusive to study using passive microrheology techniques. In this work, we employ optical tweezers and birefringent probe particles to extract the direction-resolved viscoelastic properties of the particle-laden interface. By using special types of birefringent tracer particles, we detect not only the in-plane translational mode but also the out-of-plane translational (perpendicular to the interface) and rotational modes. We first compare different passive methods of probing the viscoelasticity of the microgel laden interface of sessile drop and then study the modes perpendicular to the interface and the out-of-plane rotational mode using optical tweezers based passive microrheology. The viscoelasticity of the interface using two different methods, i.e., multiple-particle tracking passive microrheology using video microscopy and by trapping birefringent tracer particles in optical tweezers, relying on different models are studied and found to exhibit comparable trends. Interestingly, the mode orthogonal to the interface and the rotational mode also show the viscous to viscoelastic transition as the droplet evaporates, but with lesser viscoelasticity during the same evaporation time than the in-plane mode.

Bidirectional Actuation of Silk Fibroin Films: Role of Water and Alcohol Vapors.

Three-dimensional (3D) shape morphism observed in nature inspires the development of stimuli-responsive soft actuators. Vapor-responsive actuators are promising among the different stimuli-responsive materials due to their capability to produce macroscale movements in response to a minuscule amount of specific chemical vapor. Here, we report unusual multiple vapor-responsive bidirectional macroscale actuation behaviors of single-layer regenerated silk fibroin films. The vapor-responsive silk fibroin actuator exhibits antagonistic actuation characteristics in a reversible manner to both water and ethanol vapors. For instance, it produces an upward bending in the presence of water vapor and downward bending in ethanol vapor, which demonstrates the chemical vapor-specific actuation. However, the actuation characteristics remain largely invariant upon changing the polarity of alcohol molecules. The silk fibroin actuators effectively utilize the vapor-induced minuscule expansion and contraction of the film surface to produce large-scale actuation, which is fully reversible. The intrinsic water content of the films and the vapor pressure of the stimulants are exploited to control the actuation performance. Further, we demonstrated the 3D shape morphing ability of the actuator by generating an undulating wavelike motion via preprogrammed water and ethanol vapor exposure conditions. The change in the actuation direction is instantaneous, which ensures the sensitivity and rapid response of the fabricated actuators.