Nature inspired solid-liquid phase amphibious adhesive.

Here we report a new class of bio-inspired solid-liquid adhesive, obtained by simple mechanical dispersion of PVDF (polyvinylidene fluoride) (solid spheres) into PDMS (polydimethylsiloxane) (liquid). The adhesive behavior arises from strong solid-liquid interactions. This is a chemical reaction free adhesive (no curing time) that can be repeatedly used and is capable of instantaneously joining a large number of diverse materials (metals, ceramic, and polymer) in air and underwater. The current work is a significant advance in the development of amphibious multifunctional adhesives and presents potential applications in a range of sealing applications, including medical ones.

Block Copolymer Elastomer with Graphite Filler: Effect of Processing Conditions and Silane Coupling Agent on the Composite Properties.

The control of morphology and interface in poly(styrene-ethylene/butylene-styrene) (SEBS) composites with graphitic fillers is extremely important for the design of piezoresistive sensors for body motion or flexible temperature sensors. The effects of a high amount of graphite (G) and silane coupling agent on the morphology and properties of SEBS composites with anisotropic mechanical properties are reported. The physical and chemical bonding of silane to both G and SEBS surface was proved by EDX and TGA results; this improved interface influenced both the thermal and mechanical properties of the composite. The vinyltriethoxysilane (VS) promoted the formation of char residue and, being tightly bound to both SEBS and G, did not show separate decomposition peak in the TGA curve of composites. The mechanical properties were measured on two perpendicular directions and were improved by both the addition of VS and the increased amount of G; however, the increase of storage modulus due to orientation (from 5 to 15 times depending on the composition and direction of the test) was more important than that provided by the increase of G concentration, which was a maximum of four times that obtained for 15 wt % graphite. A mechanism to explain the influence of G content and treatment on the variation of storage modulus and tan δ depending on the direction of the test was also proposed.

In Situ Production of Graphene-Fiber Hybrid Structures.

We report a scalable method to obtain a new material where large graphene sheets form webs linking carbon fibers. Film-fiber hybrid nonwoven mats are formed during fiber processing and converted to carbon structures after a simple thermal treatment. This contrasts with multistep methods that attempt to mix previously prepared graphene and fibers, or require complicated and costly processes for deposition of graphene over carbon fibers. The developed graphene-fiber hybrid structures have seamless connections between graphene and fibers, and in fact the graphene "veils" extend directly from one fiber into another forming a continuous surface. The graphene-fiber hybrid structures are produced in situ from aqueous poly(vinyl alcohol) solutions. The solutions were subjected to centrifugal spinning to produce fine nanofiber mats. The addition of salt to the polymer solution stimulated a capillarity effect that promoted the formation of thin veils, which become graphene sheets upon dehydration by sulfuric acid vapor followed by carbonization (at relatively low temperatures, below 800 °C). These veils extend over several micrometers within the pores of the fiber network, and consist of crystalline graphene layers that cross-link the fibers to form a highly interconnected hybrid network. The surface area and pore diameter of the hybrid structures were measured to be 521 m2g-1 and 10 nm, respectively. The resulting structure shows high electrical conductivity, 550 S/m, and promising shielding of electromagnetic interference, making it an attractive system for a broad range of electronic applications.

Solid-Liquid Self-Adaptive Polymeric Composite.

A solid-liquid self-adaptive composite (SAC) is synthesized using a simple mixing-evaporation protocol, with poly(dimethylsiloxane) (PDMS) and poly(vinylidene fluoride) (PVDF) as active constituents. SAC exists as a porous solid containing a near equivalent distribution of the solid (PVDF)-liquid (PDMS) phases, with the liquid encapsulated and stabilized within a continuous solid network percolating throughout the structure. The pores, liquid, and solid phases form a complex hierarchical structure, which offers both mechanical robustness and a significant structural adaptability under external forces. SAC exhibits attractive self-healing properties during tension, and demonstrates reversible self-stiffening properties under compression with a maximum of 7-fold increase seen in the storage modulus. In a comparison to existing self-healing and self-stiffening materials, SAC offers distinct advantages in the ease of fabrication, high achievable storage modulus, and reversibility. Such materials could provide a new class of adaptive materials system with multifunctionality, tunability, and scale-up potentials.

Nanodiamond-based thermal fluids.

Dispersions of nanodiamond (average size ∼6 nm) within dielectric insulator mineral oil are reported for their enhanced thermal conductivity properties and potential applications in thermal management. Dynamic and kinematic viscosities-very important parameters in thermal management by nanofluids-are investigated. The dependence of the dynamic viscosity is well-described by the theoretical predictions of Einstein's model. The temperature dependence of the dynamic viscosity obeys an Arrhenius-like behavior, where the activation energy and the pre-exponential factor have an exponential dependence on the filler fraction of nanodiamonds. An enhancement in thermal conductivity up to 70% is reported for nanodiamond based thermal fluids. Additional electron microscopy, Raman spectroscopy and X-ray diffraction analysis support the experimental data and their interpretation.

Electrorheological analysis of colloidal dispersions of aluminum oxide and silicone oil.

The electrorheological properties of colloidal dispersions of aluminum oxide nanotubes and nanoparticles in silicone oil were investigated. The shear storage modulus of colloidal dispersions containing 5 wt% of aluminum oxide nanotubes increased by four orders of magnitude upon the application of an external electric field of as low as 400 V/mm. The storage modulus of the nanotube systems increased further by increasing the concentration of nanotubes. The electrorheological response of aluminum oxide nanoparticles dispersions was significantly lower than that of the dispersions containing the same weight fraction of aluminum oxide nanotubes at the same external electric field. This result reflects the effect of shape anisotropy on the electrorheological features of colloidal dispersions.

Synthesis and characterization of poly(butylene oxide) grafted carbon nanofibers.

The grafting of polybutylene oxide onto purified and functionalized carbon nanofibers is reported. Grafting was possible after the insertion of 2-(formyloxy)ethyl 2-bromo-2-methylpropanoate onto the carbon nanofibers. The polymerization of tetrahydrofuran was mediated by copper(I) bromide and 1,1,4,7-pentamethyl diethylenetriamine. The polymer-grafted carbon nanofibers were characterized by Raman spectrsocopy, Transmission Electron Microscopy, and Thermogravimetric Analysis. TEM images of CNF-COOH (A), CNF-PBO (B), completely open tip of CNF-COOH, and coated tip of CNF-PBO (D) are shown in the left panel. The right panel depicts the distribution of bromine (blue), and carbon (red) atoms inside and in the vicinity of CNF-Br (as obtained by Electron Energy Loss Spectroscopy). The bottom shows the actual doped CNF. Preliminary data showed that these modified fibers have potential applications as smart (electrorheological) fluids.

Spectroscopic investigations on epoxy--multiwall carbon nanotubes composites.

Room temperature electron spin resonance spectra of epoxy resins loaded with various concentrations of multiwalled carbon nanotubes of various lengths are analyzed. The resonance spectrum near the free electron line position is dominated by a single almost symmetric line assigned to delocalized electrons residing on multiwalled carbon nanotubes. The experimental research shown that: (1) The dependence of the g-factor on nanotubes length is controlled by the distortions of multiwalled carbon nanotubes. (2) The dependence of the g-factor on the concentration of multi-walled nanotubes reflects the interactions between electrons localized on different nanotubes. In insulating composites, the resonance line width broadens as the length and the concentration of multiwalled carbon nanotubes is increased. (3) For conducting composites, the dependence of the electron spin resonance line width on the length and concentration of multiwalled carbon nanotubes is controlled by Elliott contribution and exchange interactions, respectively. (4) The concentration of conduction electrons increases as the length and the concentration of multiwalled carbon nanotubes are increased.

A dinuclear Ni(I) system having a diradical Ni2N2 diamond core resting state: synthetic, structural, spectroscopic elucidation, and reductive bond splitting reactions.

One-electron reduction of the square-planar nickel precursor (PNP)NiCl ( 1) (PNP (-) = N[2-P(CHMe 2) 2-4-methylphenyl] 2) with KC 8 effects ligand reorganization of the pincer ligand to assemble a Ni(I) dimer, [Ni(mu 2-PNP)] 2 ( 2), containing a Ni 2N 2 core structure, as inferred by its solid-state X-ray structure. Solution magnetization measurements are consistent with a paramagnetic Ni(I) system likely undergoing a monomer <--> dimer equilibrium. The room-temperature and 4 K solid-state X-band electron paramagnetic resonance (EPR) spectra display anisotropic signals. Low-temperature solid-state X-band EPR data at 4 K reveal rhombic values g z = 1.980(4), g x = 2. 380(4), and g y = 2.225(4), as well as a forbidden signal at g = 4.24 for the Delta M S = 2 half field transition, in accord with 2 having two weakly interacting metal centers. Utilizing an S = 1 model, full spin Hamiltonian simulation of the low-temperature EPR spectrum on the solid sample was achieved by applying a nonzero zero-field-splitting parameter ( D = 0.001 cm (-1)), which is consistent with an S = 0 ground state with a very closely lying S = 1 state. Solid-state magnetization data also corroborate well with our solid-state EPR data and reveal weak antiferromagnetic behavior ( J = -1.52(5) cm (-1)) over a 2-300 K temperature range at a field of 1 Tesla. Evidence for 2 being a masked "(PNP)Ni" scaffold originates from its reaction with N 2CPh 2, which traps the Ni(I) monomer in the form of a T-shaped species, Ni(PNPNNCPh 2), a system that has been structurally characterized. The radical nature of complex 2, or its monomer component, is well manifested through the plethora of cooperative H-X-type bond cleavage reactions, providing the nickel(II) hydride (PNP)NiH and the corresponding rare functionalities -OH, -OCH 3, -PHPh, and -B(catechol) integrated into the (PNP)Ni moiety in equal molar amounts. In addition to splitting H 2, compound 2 can also engage in homolytic X-X bond cleavage reactions of PhXXPh to form (PNP)Ni(XPh) (X = S or Se).