Yachin Cohen

Strong, Light, Multifunctional Fibers of Carbon Nanotubes with Ultrahigh Conductivity

Optimizing Carbon Nanotubes Shorter carbon nanotubes are easier to make, but, when assembled into fibers, the resulting fiber properties are much poorer than might be predicted by theory. Conversely, longer carbon nanotubes have much better properties but are harder to process. Behabtu et al. (p. 182) combined the best of both worlds through scalable wet spinning method, in which they dissolved longer carbon nanotubes and then spun them into fibers that showed excellent strength, stiffness, and thermal conductivity. Exceptional carbon nanotube fibers are produced by a wet spinning process using longer nanotubes as feedstock. Broader applications of carbon nanotubes to real-world problems have largely gone unfulfilled because of difficult material synthesis and laborious processing. We report high-performance multifunctional carbon nanotube (CNT) fibers that combine the specific strength, stiffness, and thermal conductivity of carbon fibers with the specific electrical conductivity of metals. These fibers consist of bulk-grown CNTs and are produced by high-throughput wet spinning, the same process used to produce high-performance industrial fibers. These scalable CNT fibers are positioned for high-value applications, such as aerospace electronics and field emission, and can evolve into engineered materials with broad long-term impact, from consumer electronics to long-range power transmission.

Spontaneous high-concentration dispersions and liquid crystals of graphene

Graphene combines unique electronic properties and surprising quantum effects with outstanding thermal and mechanical properties. Many potential applications, including electronics and nanocomposites, require that graphene be dispersed and processed in a fluid phase. Here, we show that graphite spontaneously exfoliates into single-layer graphene in chlorosulphonic acid, and dissolves at isotropic concentrations as high as approximately 2 mg ml(-1), which is an order of magnitude higher than previously reported values. This occurs without the need for covalent functionalization, surfactant stabilization, or sonication, which can compromise the properties of graphene or reduce flake size. We also report spontaneous formation of liquid-crystalline phases at high concentrations ( approximately 20-30 mg ml(-1)). Transparent, conducting films are produced from these dispersions at 1,000 Omega square(-1) and approximately 80% transparency. High-concentration solutions, both isotropic and liquid crystalline, could be particularly useful for making flexible electronics as well as multifunctional fibres.

Characterization of glucose-sensitive insulin release systems in simulated in vivo conditions

We studied the glucose-responsive insulin controlled release system based on the hydrogel poly(2-hydroxyethyl methacrylate-co-N,N-dimethylaminoethyl methacrylate), also called poly(HEMA-co-DMAEMA), with entrapped glucose oxidase, catalase and insulin. When exposed to physiological fluids, glucose diffuses into the hydrogel, glucose oxidase catalyzes the glucose conversion to gluconic acid, causing swelling of the pH-sensitive hydrogel and subsequently increased insulin release. The higher the glucose concentration in the medium, the higher and faster the swelling and release rates. The effects of polymer morphology and oxygen availability on hydrogel swelling and on insulin release kinetics were tested. Polymer morphology was modified by changing the crosslinking agent (tetraethylene glycol dimethacrylate) concentration (0-0.95 vol%). Oxygen availability was modified by changing the immobilized catalase concentration (0-15 units catalase per unit glucose oxidase) and by bubbling oxygen through the medium. The results indicated that: (i) Hydrogels without crosslinking agent were found to be stable in water, and their sensitivity to pH and glucose was higher than the chemically crosslinked hydrogels. (ii) Immobilization of catalase in addition to glucose oxidase in hydrogels prepared without crosslinking agent, resulted in enhanced swelling kinetic. In addition, we carried out primary in vivo experiments on rats, which demonstrated that at least some of the entrapped insulin retains its active form and is effective in reducing blood glucose levels. Moreover, no tissue encapsulation was observed around matrices implanted in the peritoneum. In conclusion, the pH-sensitive hydrogel poly(HEMA-co-DMAEMA) can be manipulated to produce glucose-responsive insulin release system that is effective in reducing blood glucose levels.

The effect of embedded carbon nanotubes on the morphological evolution during the carbonization of poly(acrylonitrile) nanofibers

Hybrid nanofibers with different concentrations of multi-walled carbon nanotubes (MWCNTs) in polyacrylonitrile (PAN) were fabricated using the electrospinning technique and subsequently carbonized. The morphology of the fabricated carbon nanofibers (CNFs) at different stages of the carbonization process was characterized by transmission electron microscopy and Raman spectroscopy. The polycrystalline nature of the CNFs was shown, with increasing content of ordered crystalline regions having enhanced orientation with increasing content of MWCNTs. The results indicate that embedded MWCNTs in the PAN nanofibers nucleate the growth of carbon crystals during PAN carbonization.

Spontaneous dissolution of ultralong single- and multiwalled carbon nanotubes.

We report that chlorosulfonic acid is a true solvent for a wide range of carbon nanotubes (CNTs), including single-walled (SWNTs), double-walled (DWNTs), multiwalled carbon nanotubes (MWNTs), and CNTs hundreds of micrometers long. The CNTs dissolve as individuals at low concentrations, as determined by cryo-TEM (cryogenic transmission electron microscopy), and form liquid-crystalline phases at high concentrations. The mechanism of dissolution is electrostatic stabilization through reversible protonation of the CNT side walls, as previously established for SWNTs. CNTs with highly defective side walls do not protonate sufficiently and, hence, do not dissolve. The dissolution and liquid-crystallinity of ultralong CNTs are critical advances in the liquid-phase processing of macroscopic CNT-based materials, such as fibers and films.

A novel composite based on ultra-high-molecular-weight polyethylene

Abstract A novel composite material consisting of ultra-high-molecular-weight polyethylene (UHMWPE) fibers and matrix has been prepared, characterized and shown to possess unique properties, in particular an elongation of over 70% in the direction transverse to the fibers which induces transverse orientation of the matrix. This indicates that excellent adhesion between fibers and matrix has been achieved in this composite material which exhibits the unique properties of the UHMWPE matrix.

Precursors of the zeolite ZSM-5 imaged by Cryo-TEM and analyzed by SAXS

The microstructural evolution in the nucleation stage of a synthesis reaction of ZSM-5 zeolite was studied, with particular emphasis on the role of the organic cation, TPA+ (tetrapropylammonium). Direct observation of the microstructure was achieved by cryo-transmission electron microscopy (cryo-TEM). The quantitative evaluation of the structural units was obtained by small-angle X-ray scattering (SAXS) measurements. In the presence of the organic cation TPA+, we found globular structural units 5 nm in diameter that aggregate to elongated bodies 44 nm long. The globular structural units were found in reaction mixtures with or without the organic template TPA-OH, as long as the pH of the initial solution was kept above 11.6. Without TPA+, aggregation to cylindrical particles was not observed after 2 h of heating, and no ZSM-5 crystallinity was attained at the end of the reaction (after 8 d). These results suggest that the zeolite ZSM-5 building blocks are globular structural units, 5 nm in diameter, containing silica, alumina, organic cation, and water, which fuse together to produce elongated aggregates that may compose the final unit cell. It is concluded that the globular structural unit is a cluster of tetrapods similar to those found in the final ZSM-5 crystals.

Interactions between block copolymers and single-walled carbon nanotubes in aqueous solutions: a small-angle neutron scattering study.

The amphiphilic copolymers of the Pluronic family are known to be excellent dispersants for single-walled carbon nanotubes (SWCNT) in water, especially F108 and F127, which have rather long end-blocks of poly(ethylene oxide) (PEO). In this study, the structure of the CNT/polymer hybrid formed in water is evaluated by measurements of small-angle neutron scattering (SANS) with contrast variation, as supported by cryo-transmission electron microscopy (cryo-TEM) imaging. The homogeneous, stable, inklike dispersions exhibited very small isolated bundles of carbon nanotubes in cryo-TEM images. SANS experiments were conducted at different D(2)O/H(2)O content of the dispersing solvent. The data for both systems showed surprisingly minimal intensity values at 70% D(2)O solvent composition, which is much higher than the expected value of 17% D(2)O that is based on the scattering length density (SLD) of PEO. At this near match point, the data exhibited a q(-1) power law relation of intensity to the scattering vector (q), indicating rodlike entities. Two models are evaluated, as extensions to Pedersons block copolymer micelles models. One is loosely adsorbed polymer chains on a rodlike CNT bundle. In the other, the hydrophobic block is considered to form a continuous hydrated shell on the CNT surface, whereas the hydrophilic blocks emanate into the solvent. Both models were found to fit the experimental data reasonably well. The model fit required special considerations of the tight association of water molecules around PEO chains and slight isotopic selectivity.

True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures

Evidence is presented for the first time of true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with ionic liquid. Cryogenic transmission electron microscopy, small-angle neutron-, X-ray- and static light scattering were used to investigate the structure of cellulose solutions in mixture of dimethyl formamide and 1-ethyl-3-methylimidazolium acetate. Structural information on the dissolved chains (average molecular weight ∼ 5 × 10(4)g/mol; gyration radius ∼ 36 nm, persistence length ∼ 4.5 nm), indicate the absence of significant aggregation of the dissolved chains and the calculated value of the second virial coefficient ∼ 2.45 × 10(-2)mol ml/g(2) indicates that this solvent system is a good solvent for cellulose. More facile dissolution of cellulose could be achieved in solvent mixtures that exhibit the highest electrical conductivity. Highly concentrated cellulose solution in pure ionic liquid (27 wt.%) prepared according to novel method, utilizing the rapid evaporation of a volatile co-solvent in binary solvent mixtures at superheated conditions, shows insignificant cellulose molecular aggregation.

Tailoring the interface in polyethylene fiber/matrix composites: surface-entangled interfacial layer

The material properties of ultra-high molecular weight polyethylene (UHMWPE) and of high-performance fibers fabricated from, it are unique among polymeric materials which exhibit high modulus and strength. However, the joint utilization of UHMWPE fibers and matrix in a composite, suffers from several drawbacks. Most notable is the poor adhesion between fibers and matrix. We investigate a physical method for improvement of the interfacial adhesion between UHMWPE fibers and matrix, based on the formation of an interfacial layer, which is physically entangled with the surface of the fiber and crystallized on it together with the matrix material. As a result, strong interfacial adhesion is obtained, which allows utilization of all-UHMWPE composites having unique properties.