Functionality integration in stereolithography 3D printed microfluidics using a "print-pause-print" strategy.

Stereolithography 3D printing, although an increasingly used fabrication method for microfluidic chips, has the main disadvantage of producing monolithic chips in a single material. We propose to incorporate during printing various objects using a "print-pause-print" strategy. Here, we demonstrate that this novel approach can be used to incorporate glass slides, hydrosoluble films, paper pads, steel balls, elastic or nanoporous membranes and silicon-based microdevices, in order to add microfluidic functionalities as diverse as valves, fluidic diodes, shallow chambers, imaging windows for bacteria tracking, storage of reagents, blue energy harvesting or filters for cell capture and culture.

Line Tension in a Thick Soap Film.

The thickness of freshly made soap films is usually in the micron range, and interference colors make thickness fluctuations easily visible. Circular patterns of constant thickness are commonly observed, either a thin film disc in a thicker film or the reverse. In this Letter, we evidence the line tension at the origin of these circular patterns. Using a well controlled soap film preparation, we produce a piece of thin film surrounded by a thicker film. The thickness profile, measured with a spectral camera, leads to a line tension of the order of 10^{-10} N which drives the relaxation of the thin film shape, initially very elongated, toward a circular shape. A balance between line tension and air friction leads to a quantitative prediction of the relaxation process. Such a line tension is expected to play a role in the production of marginal regeneration patches, involved in soap film drainage and stability.

Foam coarsening under a steady shear: interplay between bubble rearrangement and film thinning dynamics.

Aqueous foams are unstable and age by drainage and coarsening. Today, these effects are well described, as also their impact on foam properties. In that respect, the foam viscoelastic properties evolve in time as a consequence of coarsening which tends to increase the mean bubble size. Here, we investigate the reverse coupling, and study if and how the continuous flow of a foam can impact its dynamics of coarsening. We introduce a new protocol where brief oscillatory measurements are inserted during a constant steady shear, allowing us to monitor the relative variation of the bubble size with time (obtained from the one of the elastic modulus G') as a function of the applied shear rate. It turns out that the coarsening rate is strongly impacted by the applied shear: this rate is continuously reduced above a critical shear rate, which itself decreases with the bubble size. This coarsening-rate reduction is interpreted as the result of out-of-equilibrium and shear-dependent film thicknesses, being higher than at rest. The critical shear rate, above which films are dynamically sustained at higher thickness than at equilibrium, emerges from the competition between the rate of rearrangements and the time required to drain the thick film created during the rearrangement. We thus report here a first experimental proof and measurements of out-of-equilibrium film thicknesses within a sheared foam, and of the impact this has on coarsening.

Stability of a directional Marangoni flow.

Marangoni flows result from surface-tension gradients, and these flows occur over finite distances on the surface, but the subsequent secondary flows can be observed on much larger lengthscales. These flows play major roles in various phenomena, from foam dynamics to microswimmer propulsion. We show here that if a Marangoni flow of soluble surfactants is confined laterally, the flow forms an inertial surface jet. A full picture of the flows on the surface is exhibited, and the velocity profile of the jet is predicted analytically, and is successfully compared with the experimental measurements. Moreover, this straight jet eventually destabilizes into meanders. A quantitative comparison between the theory and our experimental observations yields a very good agreement in terms of critical wavelengths. The characterization and understanding of the 2D flows generated by confined Marangoni spreading is a first step to understand the role of inertial effects in the Marangoni flows with and without confinement.

Luminescence thermometry for in situ temperature measurements in microfluidic devices.

Temperature control for lab-on-a-chip devices has resulted in the broad applicability of microfluidics to, e.g., polymerase chain reaction (PCR), temperature gradient focusing for electrophoresis, and colloidal particle synthesis. However, currently temperature sensors on microfluidic chips either probe temperatures outside the channel (resistance temperature detector, RTD) or are limited in both the temperature range and sensitivity in the case of organic dyes. In this work, we introduce ratiometric bandshape luminescence thermometry in which thermally coupled levels of Er3+ in NaYF4 nanoparticles are used as a promising method for in situ temperature mapping in microfluidic systems. The results, obtained with three types of microfluidic devices, demonstrate that temperature can be monitored inside a microfluidic channel accurately (0.34 °C) up to at least 120 °C with a spot size of ca. 1 mm using simple fiber optics. Higher spatial resolution can be realized by combining luminescence thermometry with confocal microscopy, resulting in a spot size of ca. 9 µm. Further improvement is anticipated to enhance the spatial resolution and allow for 3D temperature profiling.

Microfluidic probing of the complex interfacial rheology of multilayer capsules.

Encapsulation of chemicals using polymer membranes enables control of their transport and delivery for applications such as agrochemistry or detergency. To rationalize the design of polymer capsules, it is necessary to understand how the membranes' mechanical properties control the transport and release of the cargo. In this article, we use microfluidics to produce model polymer capsules and study in situ their behavior in controlled divergent flows. Our model capsules are obtained by assembling polymer mono and hydrogen-bonded bilayers at the surface of an oil droplet in water. We also use microfluidics to probe in situ the mechanical properties of the membranes in a controlled divergent flow generated by introducing the capsules through a constriction and then in a larger chamber. The deformation and relaxation of the capsules depend on their composition and especially on the molecular interactions between the polymer chains that form the membranes and the anchoring energy of the first layer. We develop a model and perform numerical simulations to extract the main interfacial properties of the capsules from the measurement of their deformations in the microchannels.

Engulfment control of platinum nanoparticles into oxidized silicon substrates for fabrication of dense solid-state nanopore arrays.

We found that platinum (Pt) nanoparticles, upon annealing at high temperature of 1000 °C, are engulfed into amorphous fused-silica or thermal oxide silicon substrates. The same phenomenon was previously published for gold (Au) nanoparticles. Similar to the Au nanoparticles, the engulfed Pt nanoparticles connect to the surface of the substrates through conical nanopores, and the size of the Pt nanoparticles decreases with increasing depth of the nanopores. We explain the phenomena as driven by the formation of platinum oxide by reaction of the platinum with atmospheric oxygen, with platinum oxide evaporating to the environment. We found that the use of Pt provides much better controllability than the use of Au. Due to the high vapor pressure of platinum oxide, the engulfment of the Pt nanoparticles into oxidized silicon (SiO2) substrates is faster than of Au nanoparticles. At high temperature annealing we also find that the aggregation of Pt nanoparticles on the substrate surface is insignificant. As a result, the Pt nanoparticles are uniformly engulfed into the substrates, leading to an opportunity for patterning dense nanopore arrays. Moreover, the use of oxidized Si substrates enables us to precisely control the depth of the nanopores since the engulfment of Pt nanoparticles stops at a short distance above the SiO x /Si interface. After subsequent etching steps, a membrane with dense nanopore through-holes with diameters down to sub-30 nm is obtained. With its simple operation and high controllability, this fabrication method provides an alternative for rapid patterning of dense arrays of solid-state nanopores at low-cost.

One-Step Fabrication of pH-Responsive Membranes and Microcapsules through Interfacial H-Bond Polymer Complexation.

Biocompatible microencapsulation is of widespread interest for the targeted delivery of active species in fields such as pharmaceuticals, cosmetics and agro-chemistry. Capsules obtained by the self-assembly of polymers at interfaces enable the combination of responsiveness to stimuli, biocompatibility and scaled up production. Here, we present a one-step method to produce in situ membranes at oil-water interfaces, based on the hydrogen bond complexation of polymers between H-bond acceptor and donor in the oil and aqueous phases, respectively. This robust process is realized through different methods, to obtain capsules of various sizes, from the micrometer scale using microfluidics or rotor-stator emulsification up to the centimeter scale using drop dripping. The polymer layer exhibits unique self-healing and pH-responsive properties. The membrane is viscoelastic at pH = 3, softens as pH is progressively raised, and eventually dissolves above pH = 6 to release the oil phase. This one-step method of preparation paves the way to the production of large quantities of functional capsules.

Interfacial Rheology of Hydrogen-Bonded Polymer Multilayers Assembled at Liquid Interfaces: Influence of Anchoring Energy and Hydrophobic Interactions.

We study the 2D rheological properties of hydrogen-bonded polymer multilayers assembled directly at dodecane-water and air-water interfaces using pendant drop/bubble dilation and the double-wall ring method for interfacial shear. We use poly(vinylpyrrolidone) (PVP) as a proton acceptor and a series of polyacrylic acids as proton donors. The PAA series of chains with varying hydrophobicity was fashioned from poly(acrylic acid), (PAA), polymethacrylic acid (PMAA), and a homemade hydrophobically modified polymer. The latter consisted of a PAA backbone covalently grafted with C12 moieties at 1% mol (referred to as PAA-1C12). Replacing PAA with the more hydrophobic PMAA provides a route for combining hydrogen bonding and hydrophobic interactions to increase the strength and/or the number of links connecting the polyacid chains to PVP. This systematic replacement allows for control of the ability of the monomer units inside the absorbed polymer layer to reorganize as the interface is sheared or compressed. Consequently, the interplay of hydrogen bonding and hydrophobic interactions leads to control of the resistance of the polymer multilayers to both shear and dilation. Using PAA-1C12 as the first layer improves the anchoring energy of a few monomers of the chain without changing the strength of the monomer-monomer contact in the complex layer. In this way, the layer does not resist shear but resists compression. This strategy provides the means for using hydrophobicity to control the interfacial dynamics of the complexes adsorbed at the interface of the bubbles and droplets that either elongate or buckle upon compression. Moreover, we demonstrate the pH responsiveness of these interfacial multilayers by adding aliquots of NaOH to the acidic water subphase surrounding the bubbles and droplets. Subsequent pH changes can eventually break the polymer complex, providing opportunities for encapsulation/release applications.

Interplay of Hydrogen Bonding and Hydrophobic Interactions to Control the Mechanical Properties of Polymer Multilayers at the Oil-Water Interface.

We probe the mechanical shear and compression properties of hydrogen-bonded polymer multilayers directly assembled at the oil-water interface using interfacial rheology techniques. We show that the polymer multilayers behave mechanically like a transient network, with elastic moduli that can be varied over 2 orders of magnitude by controlling the type and strength of physical interactions involved in the multilayers, which are controlled by the pH and the hydrophobicity of the polymer. Indeed, the interplay of hydrogen and hydrophobic interactions enables one to obtain a tighter and stronger network at the interface. Moreover, we show how a simple LBL process applied directly on emulsion droplets leads to encapsulation of a model oil, dodecane, as well as perfume molecules.