Microfluidic Generation of All‐Aqueous Double and Triple Emulsions

Higher order emulsions are used in a variety of different applications in biomedicine, biological studies, cosmetics, and the food industry. Conventional droplet generation platforms for making higher order emulsions use organic solvents as the continuous phase, which is not biocompatible and as a result, further washing steps are required to remove the toxic continuous phase. Recently, droplet generation based on aqueous two‐phase systems (ATPS) has emerged in the field of droplet microfluidics due to their intrinsic biocompatibility. Here, a platform to generate all‐aqueous double and triple emulsions by introducing pressure‐driven flows inside a microfluidic hybrid device is presented. This system uses a conventional microfluidic flow‐focusing geometry coupled with a coaxial microneedle and a glass capillary embedded in flow‐focusing junctions. The configuration of the hybrid device enables the focusing of two coaxial two‐phase streams, which helps to avoid commonly observed channel‐wetting problems. It is shown that this approach achieves the fabrication of higher‐order emulsions in a poly(dimethylsiloxane)‐based microfluidic device, and controls the structure of the all‐aqueous emulsions. This hybrid microfluidic approach allows for facile higher‐order biocompatible emulsion formation, and it is anticipated that this platform will find utility for generating biocompatible materials for various biotechnological applications.     

Progress Report on Phase Separation in Polymer Solutions

Polymeric porous media (PPM) are widely used as advanced materials, such as sound dampening foams, lithium‐ion batteries, stretchable sensors, and biofilters. The functionality, reliability, and durability of these materials have a strong dependence on the microstructural patterns of PPM. One underlying mechanism for the formation of porosity in PPM is phase separation, which engenders polymer‐rich and polymer‐poor (pore) phases. Herein, the phase separation in polymer solutions is discussed from two different aspects: diffusion and hydrodynamic effects. For phase separation governed by diffusion, two novel morphological transitions are reviewed: “cluster‐to‐percolation” and “percolation‐to‐droplets,” which are attributed to an effect that the polymer‐rich and the solvent‐rich phases reach the equilibrium states asynchronously. In the case dictated by hydrodynamics, a deterministic nature for the microstructural evolution during phase separation is scrutinized. The deterministic nature is caused by an interfacial‐tension‐gradient (solutal Marangoni force), which can lead to directional movement of droplets as well as hydrodynamic instabilities during phase separation.     

Capillary‐Assisted Fabrication of Biconcave Polymeric Microlenses from Microfluidic Ternary Emulsion Droplets

In this study, a simple capillary‐based approach for producing biconcave polymeric microlenses with uniform size and shape from ternary emulsion droplets is presented. Monodisperse ternary emulsion droplets (0.6–4.0 nL) are produced which contain a photocurable segment of an acrylate monomer and two non‐curable segments of silicone oil (SO) by using a microfluidic sheath‐flowing droplet generator on a glass chip. The curvature radius of the interfaces separating the droplet segments, as well as the droplet size, and production rate can be flexibly varied by changing the flow conditions of the organic and aqueous phases. Subsequently, off‐chip suspension photopolymerization yields non‐spherical polymeric microparticles with two spherical concave surfaces templated by two SO segments at random positions. By ultraviolet light irradiation of ternary droplets with two SO segments trapped by the interior wall of a cylindrical microcapillary (internal diameter: 130 μm), biconcave microlenses can be produced with two spherical concave surfaces with a common lens axis. The produced lenses are suitable for use as optical diverging lenses.     

Sequential Coalescence Enabled Two‐Step Microreactions in Triple‐Core Double‐Emulsion Droplets Triggered by an Electric Field

Advances in microfluidic emulsification have enabled the generation of exquisite multiple‐core droplets, which are promising structures to accommodate microreactions. An essential requirement for conducting reactions is the sequential coalescence of the multiple cores encapsulated within these droplets, therefore, mixing the reagents together in a controlled sequence. Here, a microfluidic approach is reported for the conduction of two‐step microreactions by electrically fusing three cores inside double‐emulsion droplets. Using a microcapillary glass device, monodisperse water‐in‐oil‐in‐water droplets are fabricated with three compartmented reagents encapsulated inside. An AC electric field is then applied through a polydimethylsiloxane chip to trigger the sequential mixing of the reagents, where the precise sequence is guaranteed by the discrepancy of the volume or conductivity of the inner cores. A two‐step reaction in each droplet is ensured by two times of core coalescence, which totally takes 20–40 s depending on varying conditions. The optimal parameters of the AC signal for the sequential fusion of the inner droplets are identified. Moreover, the capability of this technique is demonstrated by conducting an enzyme‐catalyzed reaction used for glucose detection with the double‐emulsion droplets. This technique should benefit a wide range of applications that require multistep reactions in micrometer scale.     

Nanomolar Synthesis in Droplet Microarrays with UV‐Triggered On‐Chip Cell Screening

Miniaturization and parallelization of combinatorial organic synthesis is important to accelerate the process of drug discovery while reducing the consumption of reagents and solvents. This work presents a miniaturized platform for on‐chip solid‐phase combinatorial library synthesis with UV‐triggered on‐chip cell screening. The platform is based on a nanoporous polymer coating on a glass slide, which is modified via photolithography to yield arrays of hydrophilic (HL) spots surrounded by superhydrophobic (SH) surface. The combination of HL spots and SH background enables confinement of nanoliter droplets, functioning as miniaturized reactors for the solid‐phase synthesis. The polymer serves as support for nanomolar solid‐phase synthesis, while a photocleavable linker enables the release of the synthesized compounds into the droplets containing live cells. A 588 compound library of bisamides is synthesized via a four‐component Ugi reaction on the chip and products are detected via stamping of the droplet array onto a conductive substrate and subsequent matrix‐assisted laser desorption ionization mass spectrometry. The light‐induced cleavage shows high flexibility in screening conditions by spatial, temporal, and quantitative control.     

Smart Microcapsules with Molecular Polarity‐ and Temperature‐Dependent Permeability

Microcapsules with molecule‐selective permeation are appealing as microreactors, capsule‐type sensors, drug and cell carriers, and artificial cells. To accomplish molecular size‐ and charge‐selective permeation, regular size of pores and surface charges have been formed in the membranes. However, it remains an important challenge to provide advanced regulation of transmembrane transport. Here, smart microcapsules are designed that provide molecular polarity‐ and temperature‐dependent permeability. With capillary microfluidic devices, water‐in‐oil‐in‐water (W/O/W) double‐emulsion drops are prepared, which serve as templates to produce microcapsules. The oil shell is composed of two monomers and dodecanol, which turns to a polymeric framework whose continuous voids are filled with dodecanol upon photopolymerization. One of the monomers provides mechanical stability of the framework, whereas the other serves as a compatibilizer between growing polymer and dodecanol, preventing macrophase separation. Above melting point of dodecanol, molecules that are soluble in the molten dodecanol are selectively allowed to diffuse across the shell, where the rate of transmembrane transport is strongly influenced by partition coefficient. The rate is drastically lowered for temperatures below the melting point. This molecular polarity‐ and temperature‐dependent permeability renders the microcapsules potentially useful as drug carriers for triggered release and contamination‐free microreactors and microsensors.     

A Microfluidic Strategy for Controllable Generation of Water‐in‐Water Droplets as Biocompatible Microcarriers

Droplet microfluidics has been widely applied in functional microparticles fabricating, tissue engineering, and drug screening due to its high throughput and great controllability. However, most of the current droplet microfluidics are dependent on water‐in‐oil (W/O) systems, which involve organic reagents, thus limiting their broader biological applications. In this work, a new microfluidic strategy is described for controllable and high‐throughput generation of monodispersed water‐in‐water (W/W) droplets. Solutions of polyethylene glycol and dextran are used as continuous and dispersed phases, respectively, without any organic reagents or surfactants. The size of W/W droplets can be precisely adjusted by changing the flow rate of dispersed and continuous phases and the valve switch cycle. In addition, uniform cell‐laden microgels are fabricated by introducing the alginate component and rat pancreatic islet (β‐TC6) cell suspension to the dispersed phase. The encapsulated islet cells retain high viability and the function of insulin secretion after cultivation for 7 days. The high‐throughput droplet microfluidic system with high biocompatibility is stable, controllable, and flexible, which can boost various chemical and biological applications, such as bio‐oriented microparticles synthesizing, microcarriers fabricating, tissue engineering, etc.     

Nanoscale Behavior and Manipulation of the Phase Transition in Single‐Crystal Cu2Se

Phase transition is a fundamental physical phenomenon that has been widely studied both theoretically and experimentally. According to the Landau theory, the coexistence of high‐ and low‐temperature phases is thermodynamically impossible during a second‐order phase transition in a bulk single crystal. Here, the coexistence of two (α and β) phases in wedge‐shaped nanosized single‐crystal Cu₂Se over a large temperature range are demonstrated. By considering the surface free‐energy difference between the two phases and the shape effect, a thermodynamic model is established, which explicitly explains their coexistence. Intriguingly, it is found that with a precise control of the heating temperature, the phase boundary can be manipulated at atomic level. These discoveries extend the understanding of phase transitions to the nanoscale and shed light on rational manipulation of phase transitions in nanomaterials.     

A domain‐decomposition strategy for a compressible multi‐phase flow interacting with a structure

The problem of a high‐pressure gas cavity and its interaction with surrounding liquid and a close‐by structure is examined numerically. Even though this is of interest in many practical applications, here, the focus is on an underwater explosion. A one‐way DD strategy coupling a radial and a 3D solver for compressible multiphase flows is proposed, and the different components are successfully validated. This is a time‐space DD, which assumes the explosion that occurs sufficiently far from boundaries. It means that the radial solution is used everywhere until radial symmetry is no more applicable. When acoustic waves reach a close structure, the radial solution initiates the 3D solution near the body and continues to be applied only far from the structure and to provide the boundary conditions for the 3D sub‐domain. The advantage is to limit the computational costs and preserve reliability and accuracy. The radial solution could be applied to assess local damages during the initial acoustic phase; the time‐space DD needs to be used to investigate both local and global consequences on the vessels. The structure is modeled both as a rigid wall and as an orthotropic plate, which provides a good representation of the bottom grillages of ships. Copyright © 2014 John Wiley & Sons, Ltd.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

In Situ Observation of Single‐Phase Lithium Intercalation in Sub‐25‐nm Nanoparticles

Many lithium‐storage materials operate via first‐order phase transformations with slow kinetics largely restricted by the nucleation and growth of a new phase. Due to the energy penalties associated with interfaces between coexisting phases, the tendency for a single‐phase solid‐solution pathway with exceptional reaction kinetics has been predicted to increase with decreasing particle size. Unfortunately, phase evolutions inside such small particles (tens of nanometers) are often shrouded by electrode‐scale inhomogeneous reactions containing millions of particles, leading to intensive debate over the size‐dependent microscopic reaction mechanisms. This study provides a generally applicable methodology capable of tracking lithiation pathways in individual nanoparticles and unambiguously reveals that lithiation of anatase TiO₂, previously long believed to be biphasic, converts to a single‐phase reaction when particle size reaches ≈25 nm. These results imply the prevalence of such a size‐dependent transition in lithiation mechanism among intercalation compounds and provide important guidelines for designing high‐power electrodes, especially cathodes.     

Multi‐Step Crystallization of Self‐Organized Spiral Eutectics

A method for the solidification of metallic alloys involving spiral self‐organization is presented as a new strategy for producing large‐area chiral patterns with emergent structural and optical properties, with attention to the underlying mechanism and dynamics. This study reports the discovery of a new growth mode for metastable, two‐phase spiral patterns from a liquid metal. Crystallization proceeds via a non‐classical, two‐step pathway consisting of the initial formation of a polytetrahedral seed crystal, followed by ordering of two solid phases that nucleate heterogeneously on the seed and grow in a strongly coupled fashion. Crystallographic defects within the seed provide a template for spiral self‐organization. These observations demonstrate the ubiquity of defect‐mediated growth in multi‐phase materials and establish a pathway toward bottom‐up synthesis of chiral materials with an inter‐phase spacing comparable to the wavelength of infrared light. Given that liquids often possess polytetrahedral short‐range order, our results are applicable to many systems undergoing multi‐step crystallization.     

Spontaneous Growth and Division in Self‐Reproducing Inorganic Colloidosomes

Self‐reproduction in compartmentalized chemical ensembles is a central issue for the development of new materials and processes capable of autonomous behavior, self‐amplification and artificial evolution. Current approaches to synthetic cellularity focus primarily on self‐assembled soft matter systems such as membrane‐bounded lipid vesicles, which have sufficient structural plasticity to undergo growth and division. Steps towards inorganic protocells are being advanced, but self‐reproduction in these more structurally robust micro‐compartments has not been demonstrated. Here, a primitive form of growth and division involving inorganic colloidosomes (Pickering emulsions), comprising aqueous micro‐droplets enclosed by an ultrathin membrane of silica nanoparticles, is shown. Growth of the colloidosomes is induced by organosilane‐mediated methanol formation, and results in a localized rupture of the inorganic membrane followed by outgrowth and separation of a second‐generation protocell, which is stabilized by de novo nanoparticle assembly. These observations provide a first step towards synthetic cell‐like inorganic materials capable of chemically induced self‐reproduction.     

Temperature‐Controlled High‐Speed AFM: Real‐Time Observation of Ripple Phase Transitions

With nanometer lateral and Angstrom vertical resolution, atomic force microscopy (AFM) has contributed unique data improving the understanding of lipid bilayers. Lipid bilayers are found in several different temperature‐dependent states, termed phases; the main phases are solid and fluid phases. The transition temperature between solid and fluid phases is lipid composition specific. Under certain conditions some lipid bilayers adopt a so‐called ripple phase, a structure where solid and fluid phase domains alternate with constant periodicity. Because of its narrow regime of existence and heterogeneity ripple phase and its transition dynamics remain poorly understood. Here, a temperature control device to high‐speed atomic force microscopy (HS‐AFM) to observe dynamics of phase transition from ripple phase to fluid phase reversibly in real time is developed and integrated. Based on HS‐AFM imaging, the phase transition processes from ripple phase to fluid phase and from ripple phase to metastable ripple phase to fluid phase could be reversibly, phenomenologically, and quantitatively studied. The results here show phase transition hysteresis in fast cooling and heating processes, while both melting and condensation occur at 24.15 °C in quasi‐steady state situation. A second metastable ripple phase with larger periodicity is formed at the ripple phase to fluid phase transition when the buffer contains Ca²⁺. The presented temperature‐controlled HS‐AFM is a new unique experimental system to observe dynamics of temperature‐sensitive processes at the nanoscopic level.     

Fatigue crack propagation under in‐phase and out‐of‐phase biaxial loading

Fatigue damage characteristics of aluminium alloy under complex biaxial loads such as in‐phase and out‐of‐phase loading conditions and different biaxiality ratios have been investigated. The effects of microscale phenomena on macroscale crack growth were studied to develop an in‐depth understanding of crack nucleation and growth. Material characterization was conducted to study the microstructure variability. Scanning electron microscopy was used to identify the second phase particles, and energy dispersive X‐ray spectroscopy was performed to analyse their phases and elements. Extensive quasi‐static and fatigue tests were conducted on Al7075‐T651 cruciform specimens over a wide range of load ratios and phases. Detailed fractography analysis was conducted to understand the crack growth behaviour observed during the fatigue tests. Significant differences in crack initiation and propagation behaviour were observed when a phase difference was applied. Primarily, crack retardation and splitting were observed because of the constantly varying mode mixity caused by phase difference. The crack growth behaviour and fatigue lives under out‐of‐phase loading were compared with those under in‐phase loading to understand the effect of mixed‐mode fracture.     

Synthesis of Colloidal SU‐8 Polymer Rods Using Sonication

The bulk synthesis of fluorescent colloidal SU‐8 polymer rods with tunable dimensions is described. The colloidal SU‐8 rods are prepared by shearing an emulsion of SU‐8 polymer droplets and then exposing the resulting non‐Brownian rods to ultrasonic waves, which breaks them into colloidal rods with typical lengths of 3.5–10 µm and diameters of 0.4–1 µm. The rods are stable in both aqueous and apolar solvents, and by varying the composition of apolar solvent mixtures both the difference in refractive index and mass density between particles and solvent can be independently controlled. Consequently, these colloidal SU‐8 rods can be used in both 3D confocal microscopy and optical trapping experiments while carefully tuning the effect of gravity. This is demonstrated by using confocal microscopy to image the liquid crystalline phases and the isotropic–nematic interface formed by the colloidal SU‐8 rods and by optically trapping single rods in water. Finally, the simultaneous confocal imaging and optical manipulation of multiple SU‐8 rods in the isotropic phase is shown.     

A Gibbs‐energy‐barrier‐based computational micro‐sphere model for the simulation of martensitic phase‐transformations

We introduce a material model for the simulation of polycrystalline materials undergoing solid‐to‐solid phase‐transformations. As a basis, we present a scalar‐valued phase‐transformation model where a Helmholtz free energy function depending on volumetric and deviatoric strain measures is assigned to each phase. The analysis of the related overall Gibbs energy density allows for the calculation of energy barriers. With these quantities at hand, we use a statistical‐physics‐based approach to determine the resulting evolution of volume fractions. Though the model facilitates to take into account an arbitrary number of solid phases of the underlying material, we restrict this work to the simulation of phase‐transformations between an austenitic parent phase and a martensitic tension and compression phase. The scalar model is embedded into a computational micro‐sphere formulation in view of the simulation of three‐dimensional boundary value problems. The final modelling approach necessary for macroscopic simulations is accomplished by a finite element formulation, where the local material behaviour at each integration point is governed by the response of the micro‐sphere model.Copyright © 2014 John Wiley & Sons, Ltd.     

Impurity‐Induced First‐Order Phase Transitions in Highly Crystalline V2O3 Nanocrystals

A first‐order phase transition in a bulk material is generally considered to arise at extended defects such as grain boundaries or dislocations, where the energetic barrier between the two phases is reduced. Downsizing a crystal to the nanoscale can exclude the number of defects, leading to enhanced kinetic stabilization of the metastable phase. Here, the disappearance of the first‐order metal–insulator transition in defect‐free V₂O₃ nanocrystals and the revival of the transition by introducing a certain Cr or Ti impurity content are investigated. The hysteresis width of the transition corresponding to the barrier height decreases with the impurity content. It is proposed that homogeneous impurity doping is a universal method that can control the occurrence of a first‐order phase transition in nanoscale materials.     

Superamphiphobic Bionic Proboscis for Contamination‐Free Manipulation of Nano and Core–Shell Droplets

Manipulation of nanoliter droplets is a key step for many emerging technologies including ultracompact microfluidics devices, 3D and flexible electronic printing. Despite progress, contamination‐free generation and release of nanoliter droplets by compact low‐cost devices remains elusive. In the present study, inspired by butterflies' minute manipulation of fluids, the authors have engineered a superamphiphobic bionic proboscis (SAP) layout that surpasses synthetic and natural designs. The authors demonstrate the scalable fabrication of SAPs with tunable inner diameters down to 50 µ m by the rapid gas‐phase nanotexturing of the outer and inner surfaces of readily available hypodermic needles. Optimized SAPs achieve contamination‐free manipulation of water and oil droplets down to a liquid surface tension of 26.56 mN m^?1 and a volume of 10 nL. The unique potential of this layout is showcased by the rapid and carefully controlled in‐air synthesis of core‐shell droplets with well‐controlled compositions. These findings provide a new low‐cost tool for high‐precision manipulation of nanoliter droplets, offering a powerful alternative to established thermal‐ and electrodynamic‐based devices.     

Controlling the Morphology of PVDF Hollow Fiber Membranes by Promotion of Liquid–Liquid Phase Separation

In literature, liquid–liquid (L–L) phase separation has been widely adopted as the principle technique by which polymeric membranes are produced. However, the promotion of L–L phase separation as the means of controlling membrane morphology is still debatable. Thus, this work aims to introduce a facile and cost‐effective technique for controlling the morphology of poly(vinylidene fluoride) (PVDF) hollow fiber membranes (HFMs). The proposed technique is based on promotion of L–L phase separation which can be achieved through two different approaches: 1) reducing the distance between locations of dope and binodal curve through locating spinning dope on nonsolvent (water)/solvent (2‐pyrrolidone)/polymer (PVDF) ternary phase diagram by increasing of nonsolvent content and maintaining of polymer concentration at initial level; 2) simultaneous occurrence of thermally and nonsolvent induced phase separation (TNIPS). It is found that L–L phase separation promotion based on the above described approaches yields to PVDF HFM with partially double‐layered structure, enhanced mechanical properties, higher porosity, and smaller average pore radius with the potential to purify textile wastewater containing C.I. Disperse Violet 33. The proposed technique is advantageous due to lack of need for additives or post‐treatment process for HFM synthesis.