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1. Measurement of the surface hydrophobicity of engineered nanoparticles using an atomic force microscope

   https://doi.org/10.1039/c8cp04676j  

   Fu, Wanyi ; Zhang, Wen ( January 2018 , Physical Chemistry Chemical Physics)

   Determination of the surface hydrophobicity or wettability of nanomaterials and nanoparticles (NPs) is often challenged by the heterogeneous properties of NPs that vary with particle size, shape, surface charge, aggregation states, and surface sorption or coating. This study first summarized inherent limitations of the water contact angle, octanol–water partition coefficient ( K ow ) and surface adsorption of probe molecules in probing nanomaterial hydrophobicity. Then, we demonstrated the principle of a scanning probe method based on atomic force microscopy (AFM) for the local surface hydrophobicity measurement. Specifically, we measured the adhesion forces between functionalized AFM tips and self-assembled monolayers (SAMs) to establish a linear relationship between the adhesion forces and water contact angles based on the continuum thermodynamic approach (CTA). This relationship was used to determine the local surface hydrophobicity of seven different NPs ( i.e. , TiO 2 , ZnO, SiO 2 , CuO, CeO 2 , α-Fe 2 O 3 , and Ag), which agreed well with bulk contact angles of these NPs. Some discrepancies were observed for Fe 2 O 3 , CeO 2 and SiO 2 NPs, probably because of surface hydration and roughness effects. Moreover, the solution pH and ionic strength had negligible effects onmore »the adhesion forces between the AFM tip and MWCNTs or C 60 , indicating that the hydrophobicity of carbonaceous nanomaterials is not influenced by pH or ionic strength (IS). By contrast, natural organic matter (NOM) appreciably decreased the hydrophobicity of MWCNTs and C 60 due to surface coating of hydrophilic NOM. This scanning probe method has been proved to be reliable and robust toward the accurate measurement of the nanoscale hydrophobicity of individual NPs or nanomaterials in liquid environments.« less
2. Microgel and coacervate formation in polyelectrolyte​/multivalent ion mixtures

   Lapitsky, Y. ( August 2017 , Abstracts of Papers, 254th ACS National Meeting & Exposition)

   When polyelectrolytes and oppositely-charged multivalent ions are mixed in aqueous solutions, they can self-assemble into an array of soft materials and complex fluids, ranging from micro- and nanoparticles, to coacervates, to macroscopic gels. Here, we describe the formation and useful/interesting properties of two such materials: (1) submicron particles formed via ionotropic gelation of the cationic polysaccharide chitosan with tripolyphosphate (TPP); and (2) coacervates prepared from mixtures of the synthetic polycation poly(allylamine hydrochloride) (PAH) with either TPP or pyrophosphate (PPi). For chitosan/TPP particles (which are widely explored as potential drug carriers) we show how, by inhibiting chitosan/TPP binding, monovalent salt (NaCl) can be used to: (1) drastically slow down the rapid ionotropic gelation process to facilitate the experimental analysis of how these particles form; (2) enhance the stability of these particles to aggregation; and (3) achieve improved control over particle size. Unlike the gel-like chitosan/TPP ionic networks, which are both soft (with 10^3 - 10^4 Pa storage moduli) and water-rich, mixtures of PAH with TPP and PPi form high-modulus, putty-like coacervates with storage moduli above 10^5 Pa and much lower (26 - 40 wt%) water contents. These moduli and water contents evidently reflect the high ionic crosslink densities enabled by themore »densely-charged and flexible PAH chains, and strong PAH/PPi and PAH/TPP binding (which also imparts these coacervates with long relaxation times). Besides their bulk properties, we show that the coacervates adhere to diverse substrates (both hydrophilic and hydrophobic) and, when used as wet adhesives, deliver short-term tensile adhesion strengths above 10^5 Pa. Further, the dense crosslinking within PAH/PPi and PAH/TPP coacervates makes them strong barriers to solute diffusion and (regardless of the solute-coacervate binding strength) enables them to release small water-soluble molecules over multiple months. These findings suggest that PAH/PPi and PAH/TPP coacervates can provide a simple route to both underwater adhesion and long-term controlled release.« less
3. Dispersing nano- and micro-sized portlandite particulates via electrosteric exclusion at short screening lengths

   https://doi.org/10.1039/D0SM00045K  

   Timmons, Jason ; Mehdipour, Iman ; Gao, Shang ; Atahan, Hakan ; Neithalath, Narayanan ; Bauchy, Mathieu ; Garboczi, Edward ; Srivastava, Samanvaya ; Sant, Gaurav ( April 2020 , Soft Matter)

   In spite of their high surface charge (zeta potential ζ = +34 mV), aqueous suspensions of portlandite (calcium hydroxide: Ca(OH) 2 ) exhibit a strong tendency to aggregate, and thereby present unstable suspensions. While a variety of commercial dispersants seek to modify the suspension stability and rheology ( e.g. , yield stress, viscosity), it remains unclear how the performance of electrostatically and/or electrosterically based additives is affected in aqueous environments having either a high ionic strength and/or a pH close to the particle's isoelectric point (IEP). We show that the high native ionic strength (pH ≈ 12.6, IEP: pH ≈ 13) of saturated portlandite suspensions strongly screens electrostatic forces (Debye length: κ −1 = 1.2 nm). As a result, coulombic repulsion alone is insufficient to mitigate particle aggregation and affect rheology. However, a longer-range geometrical particle–particle exclusion that arises from electrosteric hindrance caused by the introduction of comb polyelectrolyte dispersants is very effective at altering the rheological properties and fractal structuring of suspensions. As a result, comb-like dispersants that stretch into the solvent reduce the suspension's yield stress by 5× at similar levels of adsorption as compared to linear dispersants, thus enhancing the critical solid loading ( i.e. , atmore »which jamming occurs) by 1.4×. Significantly, the behavior of diverse dispersants is found to be inherently related to the thickness of the adsorbed polymer layer on particle surfaces. These outcomes inform the design of dispersants for concentrated suspensions that present strong charge screening behavior.« less
4. Stranger than metals

   https://doi.org/10.1126/science.abh4273  

   Phillips, Philip W. ; Hussey, Nigel E. ; Abbamonte, Peter ( July 2022 , Science)

   BACKGROUND Landau’s Fermi liquid theory provides the bedrock on which our understanding of metals has developed over the past 65 years. Its basic premise is that the electrons transporting a current can be treated as “quasiparticles”—electron-like particles whose effective mass has been modified, typically through interactions with the atomic lattice and/or other electrons. For a long time, it seemed as though Landau’s theory could account for all the many-body interactions that exist inside a metal, even in the so-called heavy fermion systems whose quasiparticle mass can be up to three orders of magnitude heavier than the electron’s mass. Fermi liquid theory also lay the foundation for the first successful microscopic theory of superconductivity. In the past few decades, a number of new metallic systems have been discovered that violate this paradigm. The violation is most evident in the way that the electrical resistivity changes with temperature or magnetic field. In normal metals in which electrons are the charge carriers, the resistivity increases with increasing temperature but saturates, both at low temperatures (because the quantized lattice vibrations are frozen out) and at high temperatures (because the electron mean free path dips below the smallest scattering pathway defined by the lattice spacing).more »In “strange metals,” by contrast, no saturation occurs, implying that the quasiparticle description breaks down and electrons are no longer the primary charge carriers. When the particle picture breaks down, no local entity carries the current. ADVANCES A new classification of metallicity is not a purely academic exercise, however, as strange metals tend to be the high-temperature phase of some of the best superconductors available. Understanding high-temperature superconductivity stands as a grand challenge because its resolution is fundamentally rooted in the physics of strong interactions, a regime where electrons no longer move independently. Precisely what new emergent phenomena one obtains from the interactions that drive the electron dynamics above the temperature where they superconduct is one of the most urgent problems in physics, attracting the attention of condensed matter physicists as well as string theorists. One thing is clear in this regime: The particle picture breaks down. As particles and locality are typically related, the strange metal raises the distinct possibility that its resolution must abandon the basic building blocks of quantum theory. We review the experimental and theoretical studies that have shaped our current understanding of the emergent strongly interacting physics realized in a host of strange metals, with a special focus on their poster-child: the copper oxide high-temperature superconductors. Experiments are highlighted that attempt to link the phenomenon of nonsaturating resistivity to parameter-free universal physics. A key experimental observation in such materials is that removing a single electron affects the spectrum at all energy scales, not just the low-energy sector as in a Fermi liquid. It is observations of this sort that reinforce the breakdown of the single-particle concept. On the theoretical side, the modern accounts that borrow from the conjecture that strongly interacting physics is really about gravity are discussed extensively, as they have been the most successful thus far in describing the range of physics displayed by strange metals. The foray into gravity models is not just a pipe dream because in such constructions, no particle interpretation is given to the charge density. As the breakdown of the independent-particle picture is central to the strange metal, the gravity constructions are a natural tool to make progress on this problem. Possible experimental tests of this conjecture are also outlined. OUTLOOK As more strange metals emerge and their physical properties come under the scrutiny of the vast array of experimental probes now at our disposal, their mysteries will be revealed and their commonalities and differences cataloged. In so doing, we should be able to understand the universality of strange metal physics. At the same time, the anomalous nature of their superconducting state will become apparent, offering us hope that a new paradigm of pairing of non-quasiparticles will also be formalized. The correlation between the strength of the linear-in-temperature resistivity in cuprate strange metals and their corresponding superfluid density, as revealed here, certainly hints at a fundamental link between the nature of strange metallicity and superconductivity in the cuprates. And as the gravity-inspired theories mature and overcome the challenge of projecting their powerful mathematical machinery onto the appropriate crystallographic lattice, so too will we hope to build with confidence a complete theory of strange metals as they emerge from the horizon of a black hole. Curved spacetime with a black hole in its interior and the strange metal arising on the boundary. This picture is based on the string theory gauge-gravity duality conjecture by J. Maldacena, which states that some strongly interacting quantum mechanical systems can be studied by replacing them with classical gravity in a spacetime in one higher dimension. The conjecture was made possible by thinking about some of the fundamental components of string theory, namely D-branes (the horseshoe-shaped object terminating on a flat surface in the interior of the spacetime). A key surprise of this conjecture is that aspects of condensed matter systems in which the electrons interact strongly—such as strange metals—can be studied using gravity.« less
5. Chemical heterogeneity in interfacial layers of polymer nanocomposites

   https://doi.org/10.1039/c8sm00663f  

   Yang, Siyang ; Liu, Siqi ; Narayanan, Suresh ; Zhang, Chongfeng ; Akcora, Pinar ( January 2018 , Soft Matter)

   It is well-known that particle–polymer interactions strongly control the adsorption and conformations of adsorbed chains. Interfacial layers around nanoparticles consisting of adsorbed and free matrix chains have been extensively studied to reveal their rheological contribution to the behavior of nanocomposites. This work focuses on how chemical heterogeneity of the interfacial layers around the particles governs the microscopic mechanical properties of polymer nanocomposites. Low glass-transition temperature composites consisting of poly(vinyl acetate) coated silica nanoparticles in poly(ethylene oxide) and poly(methyl acrylate) matrices, and of poly(methyl methacrylate) silica nanoparticles in a poly(methyl acrylate) matrix are examined using rheology and X-ray photon correlation spectroscopy. We demonstrate that miscibility between the adsorbed and matrix chains in the interfacial layers led to the observed unusual reinforcement. We suggest that packing of chains in the interfacial regions may also contribute to the reinforcement in the polymer nanocomposites. These features may be used in designing mechanically adaptive composites operating at varying temperature.