Structural design of FeCo alloy implanted into N,S co-doped carbon nanotubes via self-catalyzed growth for advanced liquid and flexible all-state-state Zn-air battery.

The introduction of transition bimetallic alloys can effectively improve oxygen reduction reaction (ORR) activity. However, the alloy particles are inclined to dissolve under harsher conditions, resulting in a serious decrease in catalytic activity and stability. Herein, an efficient ORR catalyst, FeCo alloy nanoparticles (NPs) encapsulated in N,S co-doped carbon nanotubes (FeCo10-NSCNTs), was developed through a self-catalyzed growth strategy. Due to the delicate structural design, the N,S co-doped structure can effectively improve the ORR performance by modulating the electronic properties and surface polarity of the carbon substrate, and the randomly connected carbon nanotube structure with large specific surface area can further enhance the adsorption and dissociation of gas molecules, accelerating the kinetics of gas participation in the reaction. Carbon-encapsulated FeCo alloys are beneficial for improving catalytic activity and durability. The FeCo10-NSCNTs displayed excellent ORR activity with a half-wave potential of E1/2 = 0.84 V and robust stability of 13 k cycles. More impressively, the assembled liquid-state Zn-air battery (ZAB) with FeCo10-NSCNTs as the air-electrode delivers an output power density of 146.68 mW cm-2 along with excellent operation durability. The assembled all-solid ZAB has good cyclic stability under 0-180° bending conditions. The synthesized N,S co-doping, carbon nanotubes and FeCo alloys provide important guidance for the construction of cheap non-noble metal-carbon hybrid nanomaterials.

Single-Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2 O2 Production.

Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn-N2 O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn-N2 O2 -S). Systematic analyses demonstrate that the synergetic effects between the N2 O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2 O2 . Remarkably, the Zn-N2 O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2 O2 generation. Consequently, the Zn-N2 O2 -S SAC exhibits impressive electrochemical H2 O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm-2 in the flow cell, it shows a high H2 O2 production rate of 6.924 mol gcat -1 h-1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h.

Eco-Friendly Epoxy-Terminated Polyurethane-Modified Epoxy Resin with Efficient Enhancement in Toughness.

Polyurethane is widely used to toughen epoxy resins due to its excellent comprehensive properties and compatibility. However, some demerits of polyurethanes limit their applications, such as the harsh storage condition of isocyanate-terminated polyurethane (ITPU), the limited amount of ITPU in epoxy resin, and using solvents during the preparation of polyurethane-modified epoxy resins. To address these issues, in this study, we reported a facile and green approach for preparing epoxy-terminated polyurethane (EPU)-modified epoxy resins with different EPU contents. It was found that the toughness of the epoxy resin was significantly improved after the addition of EPU. When the EPU content was 30 wt%, the elongation at break and toughness were improved by 358.36% and 73.56%, respectively. In comparison, the toughening effect of EPU outperformed that of ITPU. Moreover, the high content of EPU did not significantly decrease the glass transition temperature and had little effect on the thermal stability of the epoxy resin.

Influence of crosslinking density on the mechanical and thermal properties of plant oil-based epoxy resin.

Plant oil-based epoxy resins are of great interest due to their ecological and economic necessity. Previous studies suggested that the crosslinking density had a considerable influence on the mechanical and thermal properties of plant oil-based epoxy resins. However, so far, the relationship between the crosslinking density and the thermo-mechanical properties of plant oil-based epoxy resins is not clear. To address this issue, model tung oil-based epoxy resins with different crosslinking densities were fabricated to investigate the influence of crosslinking density on the mechanical and thermal properties of tung oil-based epoxy resins. Results show that the tensile strength, Young's modulus, and glass transition temperature are linearly increased with increasing crosslinking density. The elongation at break and tensile toughness show nonlinear downward trends as the crosslinking density increases. The elongation at break decreases gently at first, then dramatically, and finally slowly as the crosslinking density increases. The tensile toughness declines sharply at first and then slowly with increasing crosslinking density. The relationship between the thermostability and the crosslinking density is complex, because the thermostability is determined by both the molecular structure of the curing system and the crosslinking density. These results provide some information for designing plant oil-based epoxy resins according to the requirements of their applications.

Diphenolic Acid-Derived Hyperbranched Epoxy Thermosets with High Mechanical Strength and Toughness.

Diglycidyl ether of bisphenol A (DGEBA) is a kind of widely used epoxy resin, but its thermosets normally show high brittleness and poor impact resistance due to the intrinsic rigid aromatic rings, which limit its application greatly. To avoid this drawback, we proposed a method to prepare a series of hyperbranched epoxies (HBEPs) with different molecular weights. After HBEPs were cured with methyl tetrahydrophthalic anhydride (MTHPA), characterizations were carried out to evaluate the properties of the cured HBEP samples. Testing results indicate that the hyperbranched thermosets can achieve excellent mechanical strength and toughness (tensile strength: 89.2 MPa, bending strength: 129.6 MPa, elongation at break: 6.1%, toughness: 4.5 MJ m-3, and impact strength: 6.7 kJ m-2), which are superior to those of the thermosets of commercial DGEBA (tensile strength: 81.2 MPa, bending strength: 108.2 MPa, elongation at break: 3.0%, toughness: 1.5 MJ m-3, and impact strength: 4.2 kJ m-2). In addition, HBEP with the highest molecular weight and degree of branching shows the best comprehensive mechanical properties. All hyperbranched thermosets exhibit high glass-transition temperatures (T g) and thermostability, which further illustrates the potential application value of HBEPs.

Simultaneous Measurements of Temperature and Viscosity for Viscous Fluids Using an Ultrasonic Waveguide.

The characterisation and monitoring of viscous fluids have many important applications. This paper reports a refined 'dipstick' method for ultrasonic measurement of the properties of viscous fluids. The presented method is based on the comparison of measurements of the ultrasonic properties of a waveguide that is immersed in a viscous liquid with the properties when it is immersed in a reference liquid. We can simultaneously determine the temperature and viscosity of a fluid based on the changes in the velocity and attenuation of the elastic shear waves in the waveguide. Attenuation is mainly dependent on the viscosity of the fluid that the waveguide is immersed in and the speed of the wave mainly depends on the surrounding fluid temperature. However, there is a small interdependency since the mass of the entrained viscous liquid adds to the inertia of the system and slows down the wave. The presented measurements have unprecedented precision so that the change due to the added viscous fluid mass becomes important and we propose a method to model such a 'viscous effect' on the wave propagation velocity. Furthermore, an algorithm to correct the velocity measurements is presented. With the proposed correction algorithm, the experimental results for kinematic viscosity and temperature show excellent agreement with measurements from a highly precise in-lab viscometer and a commercial resistance temperature detector (RTD) respectively. The measurement repeatability of the presented method is better than 2.0% in viscosity and 0.5% in temperature in the range from 8 to 300 cSt viscosity and 40 to 90 °C temperature.

Modelling viscous boundary layer dissipation effects in liquid surrounding individual solid nano and micro-particles in an ultrasonic field.

Upon application of ultrasonic waves to a suspension of solid particles in liquid, multiple scattering occurs at the particle/liquid interfaces leading to attenuation. It was recently shown through experimental verification that multiple scattering theory must include shear wave influences at the boundary between the liquid and solid particles in a nanofluid when the concentration of the scatterers is even as low as a few percent by volume. Herein, we consider silica spheres of 50-450 nm diameter in the long-wavelength regime to elucidate the form of the shear decay fields at the liquid/solid interface for individual particles. This is important because the overlap of these fields ultimately leads to the conversion of a compressional wave to shear waves and back into the compressional wave, the effect originating due to the density contrast between the particle and the liquid. Therefore, we examine in detail the velocity, vorticity and viscous dissipation in the shear wave field and around the silica spheres using finite element modelling, giving clarity to the viscous boundary effects. We also compare the numerical modelling to semi-analytical results.

A renewable tung oil-derived nitrile rubber and its potential use in epoxy-toughening modifiers.

In this study, a modifier (CTMA) prepared by emulsion copolymerization of tung oil fatty acid, methyl esters of tung oil fatty acid and acrylonitrile was used to toughen epoxy resins. The structural characterization of the copolymer was carried out by Fourier transform infrared spectroscopy, 1H NMR spectroscopy and high-temperature gel permeation chromatography. Mechanical testing, thermal characterization and scanning electron microscopy were conducted to investigate the properties of epoxy resin modified by the copolymer and further reveal its toughening mechanism. The results indicated that the newly synthesized copolymer effectively toughened the epoxy resin because the elongation-at-break was increased to 89.48%, the maximum toughness calculated by work before break was nearly 4.6 times that of the neat epoxy resin, and apparent shear yields and plastic deformations were observed in the morphology of the fractured surfaces. CTMA, which acts as a flexible cross-linker in the epoxy thermoset, may decrease the cross-linking density.

Synthesis and Properties of a Novel Environmental Epoxidized Glycidyl Ester of Ricinoleic Acetic Ester Plasticizer for Poly(vinyl chloride).

A novel renewable plasticizer based on castor oil, epoxidized glycidyl ester of ricinoleic acetic ester (EGERAE), was synthesized and applied into Poly(vinyl chloride) (PVC) for the first time. Its molecular structure was characterized by FT-IR and ¹H NMR. The effects of replacement of petroleum-based commercial plasticizer dioctyl phthalate (DOP) with EGERAE in poly(vinyl chloride) (PVC) films were researched. Thermal stability, dynamic mechanical property and mechanical properties of PVC films were investigated with thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and tensile tests. The results indicated that this castor oil-based plasticizer was able to improve the thermal stability of PVC blends when partially of completely substituting for DOP. Furthermore, EGERAE endowed PVC resin with enhanced flexibility. In addition, the exudation, volatility and extraction resistance characteristics of plasticizers were researched. The degradation mechanism and possible interaction between EGERAE and PVC molecules in the plasticized system were also investigated.

Experimental verification of nanofluid shear-wave reconversion in ultrasonic fields.

Here we present the verification of shear-mediated contributions to multiple scattering of ultrasound in suspensions. Acoustic spectroscopy was carried out with suspensions of silica of differing particle sizes and concentrations in water to find the attenuation at a broad range of frequencies. As the particle sizes approach the nanoscale, commonly used multiple scattering models fail to match experimental results. We develop a new model, taking into account shear mediated contributions, and find excellent agreement with the attenuation spectra obtained using two types of spectrometer. The results determine that shear-wave phenomena must be considered in ultrasound characterisation of nanofluids at even relatively low concentrations of scatterers that are smaller than one micrometre in diameter.

Supersymmetric exotic decays of the 125 GeV Higgs boson.

We reveal a set of novel decay topologies for the 125 GeV Higgs boson in supersymmetry which are initiated by its decay into a pair of neutralinos, and discuss their collider search strategies. This category of exotic Higgs decays is characterized by the collider signature: visible objects+E_{T}, with E_{T} dominantly arising from escaping dark matter particles. Their benchmark arises naturally in the Peccei-Quinn symmetry limit of the minimal supersymmetric standard model singlet extensions, which is typified by the coexistence of three light particles: singletlike scalar h_{1} and pseudoscalar a_{1}, and singlinolike neutralino χ_{1}, all with masses of ≲10 GeV, and the generic suppression of the exotic decays of the 125 GeV Higgs boson h_{2}→h_{1}h_{1}, a_{1}a_{1} and χ_{1}χ_{1}, however. As an illustration, we study the decay topology: h_{2}→χ_{1}χ_{2}, where the binolike χ_{2} decays to h_{1}χ_{1} or a_{1}χ_{1}, and h_{1}/a_{1}→ff[over ¯], with ff[over ¯]=µ^{+}µ^{-}, bb[over ¯]. In the dimuon case (m_{h_{1}/a_{1}}∼1 GeV), a statistical sensitivity of S/sqrt[B]>6σ can be achieved easily at the 8 TeV LHC, assuming σ(pp→Wh_{2})/σ(pp→Wh_{SM})Br(h_{2}→µ^{+}µ^{-}χ_{1}χ_{1})=0.1. In the bb[over ¯] case (m_{h_{1}/a_{1}}∼45 GeV), 600 fb^{-1} data at the 14 TeV LHC can lead to a statistical sensitivity of S/sqrt[B]>5σ, assuming σ(pp→Zh_{2})/σ(pp→Zh_{SM})Br(h_{2}→bb[over ¯]χ_{1}χ_{1})=0.5. These exotic decays open a new avenue for exploring new physics couplings with the 125 GeV Higgs boson at colliders.

Parallel carbon nanotube stripes in polymer thin film with remarkable conductive anisotropy.

In our previous study ( Mao et al. J. Phys. Chem. Lett. 2013 , 4 , 43 - 47 ), we proposed a novel method, that is, the shear-flow-induced hierarchical self-assembly of two-dimensional fillers (octadecylamine-functionalized graphene) into the well-ordered parallel stripes in a polymer matrix, to fabricate the anisotropic conductive materials. In this study, we extend this method to one-dimensional multiwalled carbon nanotubes (MWCNTs). Under the induction of shear flow, the dispersed poly(styrene ethylene/butadiene-styrene) (SEBS) phase and MWCNTs can spontaneously assemble into well-ordered parallel stripes in the polypropylene (PP) thin film. The electrical measurements indicate that the electrical resistivity in the direction parallel to the stripes is almost 6 orders of magnitude lower than that in the perpendicular direction, which is by far the most striking conductive anisotropy for the plastic anisotropic conductive materials. In addition, it is found that the size of the MWCNT stripe as well as the electrical property of the resulting anisotropic conductive thin film can be well-controlled by the gap of the shear cell.

Tailored Parallel Graphene Stripes in Plastic Film with Conductive Anisotropy by Shear-Induced Self-Assembly.

We present a simple but efficient route to prepare a highly anisotropic conductive plastic thin film from the polypropylene/(styrene-ethylene/butadiene-styrene) triblock copolymer/graphene blend via shear-induced self-assembly. Under the shear-flow induction, GE nanosheets dispersed in the polymer matrix can spontaneously assemble into ordered parallel stripes, which endow the materials significantly conductive anisotropy. The electrical resistivity in the direction parallel to the graphene stripes is almost four orders of magnitude lower than that which is perpendicular to the stripes. This study provides a new method for the precise control of the organization of functional nano-objects in polymer matrix, which can be widely extended to the fabrication of other multifunctional anisotropic materials of interest in various fields.