Yield Stress Enhancement of a Ternary Colloidal Suspension via the Addition of Minute Amounts of Sodium Alginate to the Interparticle Capillary Bridges.

Capillary suspensions are ternary solid-liquid-liquid systems produced via the addition of a small amount of secondary fluid to the bulk fluid that contained the dispersed solid particles. The secondary fluid could exert strong capillary forces between the particles and dramatically change the rheological properties of the suspension. So far, research has focused on capillary suspensions that consist of additive-free fluids, whereas capillary suspensions with additives, particularly those of large molecular weight that are highly relevant for industrial purposes, have been relatively less studied. In this study, we performed a systematic analysis of the properties of capillary suspensions that consist of paraffin oil (bulk phase), water (secondary phase), and α-Al2O3 microparticles (particle phase), in which the aqueous secondary phase contained an important eco-friendly polymeric binder, sodium alginate (SA). It was determined that the yield stress of the suspension increased significantly with the increase in the SA content in the aqueous secondary phase, which was attributed to the synergistic effect of the capillary force and hydrogen bonding force that may be related to the increase in the number of capillary bridges. The amounts of SA used to induce a significant change in the yield stress in this study were very small (<0.02% of the total sample volume). The addition of Ca2+ ions to the SA-containing secondary phase further increased the yield stress with possible gelation of the SA chains-in the presence of excess Ca2+ ions, however, the yield stress decreased because of the microscopic phase separation that occurred in the aqueous secondary phase. The microstructures of the sintered porous materials that were produced by using capillary suspensions as precursors were qualitatively well correlated to the rheological behavior of the precursor suspensions, suggesting a new method for the subtle control of the microstructures of porous materials using the addition of minute amounts of polymeric additives.

A Systematic Investigation on the Properties of Silica Nanoparticles "Multipoint"-Grafted with Poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic Acid) in Extreme Salinity Brines and Brine-Oil Interfaces.

Nanoparticles (NPs) may have great potential for various subsurface applications, including oil and gas recovery, reservoir imaging, and environmental remediation. One of the important challenges for these downhole applications is to achieve colloidal stability in subsurface media at high salinity and high temperature. It has been previously shown that several functional NPs "multipoint"-grafted with anionic poly(2-acrylamido-2-methyl-1-propanesulfonate-co-acrylic acid; AMPS-co-AA) exhibited remarkable colloidal stabilities in specific environments mimicking the harsh subsurface aquatic media, such as the American Petroleum Institute (API) brine. However, many important properties of such particles, other than the colloidal stabilities, must be studied in a more systematic fashion for a wide range of salt concentrations (Cs). Herein, we investigate various properties of the silica (SiO2) NPs multipoint-grafted with poly(AMPS-co-AA), SiO2-g-poly(AMPS-co-AA), in NaCl and CaCl2 solutions across a range of salinities. The brush behavior of the grafted random copolymers was investigated in both salt solutions from salt-free conditions up to extreme salinities. The particles displayed brine-oil interfacial activity with increasing Cs, stabilizing oil-in-brine emulsions as Pickering emulsifiers. A high internal phase emulsion (HIPE) with an internal oil phase of up to 80 vol % could be formed in CaCl2 solutions at high Cs, which exhibited gel-like behaviors.

mirRICH, a simple method to enrich the small RNA fraction from over-dried RNA pellets.

Techniques to isolate the small RNA fraction (<200nt) by column-based methods are commercially available. However, their use is limited because of the relatively high cost. We found that large RNA molecules, including mRNAs and rRNAs, are aggregated together in the presence of salts when RNA pellets are over-dried. Moreover, once RNA pellets are over-dried, large RNA molecules are barely soluble again during the elution process, whereas small RNA molecules (<100nt) can be eluted. We therefore modified the acid guanidinium thiocyanate-phenol-chloroform (AGPC)-based RNA extraction protocol by skipping the 70% ethanol washing step and over-drying the RNA pellet for 1 hour at room temperature. We named this novel small RNA isolation method "mirRICH." The quality of the small RNA sequences was validated by electrophoresis, next-generation sequencing, and quantitative PCR, and the findings support that our newly developed column-free method can successfully and efficiently isolate small RNAs from over-dried RNA pellets.

Interfacial Engineering for the Synergistic Enhancement of Thermal Conductivity of Discotic Liquid Crystal Composites.

To develop an advanced heat transfer composite, a deeper understanding of the interfacial correlation between matrix and filler is of paramount importance. To verify the effect of interfacial correlations on the thermal conductivity, the conductive fillers such as expanded graphite (EG) and boron nitride (BN) are introduced in the discotic liquid crystal (DLC)-based polymeric matrix. The DLC matrix exhibits better interfacial affinity with EG compared to BN because of the strong π-π interactions between EG and DLC. Thanks to its excellent interfacial affinity, the EG-DLC composites show a synergistic increment in thermal conducting performance.

Hollow polymer microcapsule embedded transparent and heat-insulating film.

We herein report a facile and scalable approach to manufacturing optically transparent and heat-insulating films by incorporating hollow poly(methyl methacrylate) microcapsules into a transparent polymeric matrix. The microcapsule was prepared via emulsion polymerization. The size of the microcapsules could be easily controlled from ∼1 to 3 µm by varying the polymerization time in a narrow size distribution. The microcapsules were then mixed with a UV-curable transparent liquid resin and cured by a subsequent light irradiation. The current approach could enhance the thermal barrier property of the films without a significant reduction in the optical transparency. The solid film possessing 30 wt% microcapsules, for example, exhibited a high visible light transmittance (∼80% as measured by UV-vis spectroscopy) and the thermal conductivity was reduced to 0.06 W mK-1, corresponding to 46% of the capsule free film. To quantify and verify this result, theoretical models describing a heat transfer in a hollow microsphere composite were used, and the model showed a good agreement with our experimental observations.

Facile Supramolecular Processing of Carbon Nanotubes and Polymers for Electromechanical Sensors.

We herein report a facile, cost-competitive, and scalable method for producing viscoelastic conductors via one-pot melt-blending using polymers and supramolecular gels composed of carbon nanotubes (CNTs), diphenylamine (DP), and benzophenone (BP). When mixed, a non-volatile eutectic liquid (EL) produced by simply blending DP with BP (1:1 molar ratio) enabled not only the gelation of CNTs (EL-CNTs) but also the dissolution of a number of commodity polymers. To make use of these advantages, viscoelastic conductors were produced via one-pot melt-blending the EL and CNTs with a model thermoplastic elastomer, poly(styrene-b-butadiene-b-styrene) (SBS, styrene 30 wt %). The resulting composites displayed an excellent electromechanical sensory along with re-mendable properties. This simple method using cost-competitive EL components is expected to provide an alternative to the use of expensive ionic liquids as well as to facilitate the fabrication of novel composites for various purposes.

Signal-Induced Release of Guests from a Photolatent Metal-Phenolic Supramolecular Cage and Its Hybrid Assemblies.

The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with CuII ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and CuII . We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non-covalent engineering of MSN surfaces that should be suitable for various applications in materials science.

Orthogonally Spin-Coated Bilayer Films for Photochemical Immobilization and Patterning of Sub-10-Nanometer Polymer Monolayers.

Versatile and spatiotemporally controlled methods for decorating surfaces with monolayers of attached polymers are broadly impactful to many technological applications. However, current materials are usually designed for very specific polymer/surface chemistries and, as a consequence, are not very broadly applicable and/or do not rapidly respond to high-resolution stimuli such as light. We describe here the use of a polymeric adhesion layer, poly(styrene sulfonyl azide-alt-maleic anhydride) (PSSMA), which is capable of immobilizing a 1-7 nm thick monolayer of preformed, inert polymers via photochemical grafting reactions. Solubility of PSSMA in very polar solvents enables processing alongside hydrophobic polymers or solutions and by extension orthogonal spin-coating deposition strategies. Therefore, these materials and processes are fully compatible with photolithographic tools and can take advantage of the immense manufacturing scalability they afford. For example, the thicknesses of covalently grafted poly(styrene) obtained after seconds of exposure are quantitatively equivalent to those obtained by physical adsorption after hours of thermal equilibration. Sequential polymer grafting steps using photomasks were used to pattern different regions of surface energy on the same substrate. These patterns spatially controlled the self-assembled domain orientation of a block copolymer possessing 21 nm half-periodicity, demonstrating hierarchical synergy with leading-edge nanopatterning approaches.

Ultrasmooth Polydopamine Modified Surfaces for Block Copolymer Nanopatterning on Flexible Substrates.

Nature has engineered universal, catechol-containing adhesives which can be synthetically mimicked in the form of polydopamine (PDA). In this study, PDA was exploited to enable the formation of block copolymer (BCP) nanopatterns on a variety of soft material surfaces. While conventional PDA coating times (1 h) produce a layer too rough for most applications of BCP nanopatterning, we found that these substrates could be polished by bath sonication in a weakly basic solution to form a conformal, smooth (root-mean-square roughness ∼0.4 nm), and thin (3 nm) layer free of large prominent granules. This chemically functionalized, biomimetic layer served as a reactive platform for subsequently grafting a surface neutral layer of poly(styrene-random-methyl methacrylate-random-glycidyl methacrylate) to perpendicularly orient lamellae-forming poly(styrene-block-methyl methacrylate) BCP. Moreover, scanning electron microscopy observations confirmed that a BCP nanopattern on a poly(ethylene terephthalate) substrate was not affected by bending with a radius of ∼0.5 cm. This procedure enables nondestructive, plasma-free surface modification of chemically inert, low-surface energy soft materials, thus overcoming many current chemical and physical limitations that may impede high-throughput, roll-to-roll nanomanufacturing.

Precision Marangoni-driven patterning.

A Marangoni flow is shown to occur when a polymer film possessing a spatially-defined surface energy pattern is heated above its glass transition to the liquid state. This can be harnessed to rapidly manufacture polymer films possessing prescribed height profiles. To quantify and verify this phenomenon, a model is described here which accurately predicts the formation, growth, and eventual dissipation of topographical features. The model predictions, based on numerical solutions of equations governing thin film dynamics with a Marangoni stress, are quantitatively compared to experimental measurements of thin polystyrene films containing photochemically patterned surface energy gradients. Good agreement between the model and the data is achieved at temperatures between 120 and 140 °C for a comprehensive range of heating times using reasonable physical properties as parameter inputs. For example, thickness variations that measure 102% of the starting film thickness are achieved in only 12 minutes of heating at 140 °C, values that are predicted by the model are within 6% and 3 min, respectively. The photochemical pattern that directed this flow possessed only a 0.2 dyne cm(-1) variation in surface tension between exposed and unexposed regions. The physical insights from the validated model suggest promising strategies to maximize the aspect ratio of the topographical features and minimize the processing time necessary to develop them.